Challenges and advances in quantum dot fluorescent probes to detect reactive oxygen and nitrogen species: a review.

PubMed

Adegoke, Oluwasesan; Forbes, Patricia B C

2015-03-03

The pathological and physiological effects of reactive oxygen and nitrogen species (ROS/RNS) have instigated increasing awareness in the scientific field with respect to the development of suitable probes for their detection. Among the various probes developed to date, semiconductor quantum dots (QDs) fluorescent probes have attracted significant attention. The unfavourable properties of ROS/RNS with respect to their detection, such as their short lifetimes and the competitive presence of various endogenous reactive species, capable of interfering with the probe in biological matrices, have hindered the effective performance of most probes as well as complicating the design of suitable probes. The development of novel QD fluorescent probes capable of circumventing these problems is thus, of scientific interest. In this review, we highlight the challenges faced, pros and cons and published developments to date, with respect to QD fluorescent probes for ROS/RNS such as H2O2, O2(·-), ·OH, HOCl, NO and ONOO(-). Copyright © 2014 Elsevier B.V. All rights reserved.

Complexes of DOTA-bisphosphonate conjugates: probes for determination of adsorption capacity and affinity constants of hydroxyapatite.

PubMed

Vitha, Tomas; Kubícek, Vojtech; Hermann, Petr; Kolar, Zvonimir I; Wolterbeek, Hubert Th; Peters, Joop A; Lukes, Ivan

2008-03-04

The adsorption on hydroxyapatite of three conjugates of a bisphosphonate and a macrocycle having C1, C2, and C3 spacers and their terbium complexes was studied by the radiotracer method using 160Tb as the label. The radiotracer-containing complex of the conjugate with the C3 spacer was used as a probe for the determination of the adsorption parameters of other bisphosphonates that lack a DOTA unit. A physicochemical model describing the competitive adsorption was successfully applied in the fitting of the obtained data. The maximum adsorption capacity of bisphosphonates containing bulky substituents is determined mainly by their size. For bisphosphonates having no DOTA moiety, the maximum adsorption capacity is determined by the electrostatic repulsion between negatively charged bisphosphonate groups. Compounds with a hydroxy or amino group attached to the alpha-carbon atom show higher affinities. Macrocyclic compounds containing a short spacer between the different bisphosphonic acid groups and the macrocyclic unit exhibit high affinities, indicating a synergic effect of the bisphosphonic and the macrocyclic groups during adsorption. The competition method described uses a well-characterized complex and allows a simple evaluation of the adsorption behavior of bisphosphonates. The application of the macrocycle-bisphosphonate conjugates allows easy radiolabeling via complexation of a suitable metal isotope.

Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO2) and adsorption of remazol reactive dye

NASA Astrophysics Data System (ADS)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali

2015-09-01

Nanoporous amorphous-MnO2 was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH3COO)2.4H2O) in 0.1 M KMnO4. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO2 bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO2. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye on 0.2g synthesized nanoporous amorphous-MnO2 showed 99 - 100% decolorization.

Accessible reactive surface area and abiotic redox reactivity of iron oxyhydroxides in acidic brines

NASA Astrophysics Data System (ADS)

Strehlau, Jennifer H.; Toner, Brandy M.; Arnold, William A.; Penn, R. Lee

2017-01-01

The reactivity of iron oxyhydroxide nanoparticles in low pH and high ionic strength solutions was quantified to assess abiotic contributions to oxidation-reduction chemistry in acidic brine environments, such as mine groundwater seepage, lakes in Western Australia, and acid mine drainage settings, which are of global interest for their environmental impacts and unique geomicrobiology. Factors expected to influence accessible and reactive surface area, including Fe(II) adsorption and aggregate size, were measured as a function of pH and CaCl2 concentration and related to the kinetics of redox reactions in aqueous suspensions of synthetic goethite (α-FeOOH), akaganeite (β-FeOOH), and ferrihydrite (Fe10O14(OH)2) nanoparticles. Aqueous conditions and iron oxyhydroxides were chosen based on characterization of natural iron-rich mine microbial mats located in Soudan Underground Mine State Park, Minnesota, USA. Quinone species were used as redox sensors because they are well-defined probes and are present in natural organic matter. Fe(II) adsorption to the iron oxyhydroxide mineral surfaces from aqueous solution was measurable only at pH values above 4 and either decreased or was not affected by CaCl2 concentration. Concentrations at or above 0.020 M CaCl2 in acetate buffer (pH 4.5) induced particle aggregation. Assessment of Fe(II) adsorption and particle aggregation in acidic brine suggested that accessible reactive surface area may be limited in acidic brines. This was supported by observations of decreasing benzoquinone reduction rate by adsorbed Fe(II) at high CaCl2 concentration. In contrast, the hydroquinone oxidation rate increased at high CaCl2 concentrations, which may be due to suppressed adsorption of Fe(II) generated by the reaction. Results suggest that iron geochemical cycling in acidic brine environments will be substantially different than for iron oxyhydroxides in low-saline waters with circumneutral pH. These findings have implications for acidic

Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

PubMed

Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

2015-08-18

Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

PubMed

Luo, Jing; Farrell, James

2013-01-01

Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE.

Surface Reactivity of Li2MnO3: First-Principles and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence; Vallverdu, Germain; Allouche, Joachim; Charles-Blin, Youn; Chotard, Jean-Noël; Ménétrier, Michel; Baraille, Isabelle

2017-12-20

This article deals with the surface reactivity of (001)-oriented Li 2 MnO 3 crystals investigated from a multitechnique approach combining material synthesis, X-ray photoemission spectroscopy (XPS), scanning electron microscopy, Auger electron spectroscopy, and first-principles calculations. Li 2 MnO 3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO 2 gas molecules on large Li 2 MnO 3 crystals to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after SO 2 adsorption show in particular that the adsorption is homogeneous at the micro- and nanoscale and involves Mn reduction, whereas first-principles calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.

Low frequency sonochemical synthesis of nanoporous amorphous manganese dioxide (MnO{sub 2}) and adsorption of remazol reactive dye

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, Siti Zubaidah; Yusop, Muhammad Rahimi; Othman, Mohamed Rozali, E-mail: rozali@ukm.edu.my

2015-09-25

Nanoporous amorphous-MnO{sub 2} was synthesized by sonochemical process (sonication) on the solid manganese (II) acetate tetrahydrate (Mn(CH{sub 3}COO){sub 2}.4H{sub 2}O) in 0.1 M KMnO{sub 4}. The product was characterized by X-ray diffraction (XRD), morphology of the material was scanned by Field Emission Scanning Electron Microscopy (FE-SEM) and absorptions of MnO{sub 2} bonding was characterized by Fourier Transform Infra-Red Spectrometer (FT-IR). Remazol reactive dye or Red 3BS, was used in the adsorption study using nanoporous amorphous-MnO{sub 2}. In batch experiment, 10 ppm of Remazol reactive dye was used and experiment was carried out at room temperature. Adsorption of Remazol dye onmore » 0.2g synthesized nanoporous amorphous-MnO{sub 2} showed 99 – 100% decolorization.« less

Real-Time Discrimination and Versatile Profiling of Spontaneous Reactive Oxygen Species in Living Organisms with a Single Fluorescent Probe.

PubMed

Zhang, Ruilong; Zhao, Jun; Han, Guangmei; Liu, Zhengjie; Liu, Cui; Zhang, Cheng; Liu, Bianhua; Jiang, Changlong; Liu, Renyong; Zhao, Tingting; Han, Ming-Yong; Zhang, Zhongping

2016-03-23

Fluorescent probes are powerful tools for the investigations of reactive oxygen species (ROS) in living organisms by visualization and imaging. However, the multiparallel assays of several ROS with multiple probes are often limited by the available number of spectrally nonoverlapping chromophores together with large invasive effects and discrepant biological locations. Meanwhile, the spontaneous ROS profilings in various living organs/tissues are also limited by the penetration capability of probes across different biological barriers and the stability in reactive in vivo environments. Here, we report a single fluorescent probe to achieve the effective discrimination and profiling of hydroxyl radicals (•OH) and hypochlorous acid (HClO) in living organisms. The probe is constructed by chemically grafting an additional five-membered heterocyclic ring and a lateral triethylene glycol chain to a fluorescein mother, which does not only turn off the fluorescence of fluorescein, but also create the dual reactive sites to ROS and the penetration capability in passing through various biological barriers. The reactions of probe with •OH and HClO simultaneously result in cyan and green emissions, respectively, providing the real-time discrimination and quantitative analysis of the two ROS in cellular mitochondria. Surprisingly, the accumulation of probes in the intestine and liver of a normal-state zebrafish and the transfer pathway from intestine-to-blood-to-organ/tissue-to-kidney-to-excretion clearly present the profiling of spontaneous •OH and HClO in these metabolic organs. In particular, the stress generation of •OH at the fresh wound of zebrafish is successfully visualized for the first time, in spite of its extremely short lifetime.

The challenges of using fluorescent probes to detect and quantify specific reactive oxygen species in living cells.

PubMed

Winterbourn, Christine C

2014-02-01

Small molecule fluorescent probes are vital tools for monitoring reactive oxygen species in cells. The types of probe available, the extent to which they are specific or quantitative and complications in interpreting results are discussed. Most commonly used probes (e.g. dihydrodichlorofluorescein, dihydrorhodamine) have some value in providing information on changes to the redox environment of the cell, but they are not specific for any one oxidant and the response is affected by numerous chemical interactions and not just increased oxidant generation. These probes generate the fluorescent end product by a free radical mechanism, and to react with hydrogen peroxide they require a metal catalyst. Probe radicals can react with oxygen, superoxide, and various antioxidant molecules, all of which influence the signal. Newer generation probes such as boronates act by a different mechanism in which nucleophilic attack by the oxidant on a blocking group releases masked fluorescence. Boronates react with hydrogen peroxide, peroxynitrite, hypochlorous acid and in some cases superoxide, so are selective but not specific. They react with hydrogen peroxide very slowly, and kinetic considerations raise questions about how the reaction could occur in cells. Data from oxidant-sensitive fluorescent probes can provide some information on cellular redox activity but is widely misinterpreted. Recently developed non-redox probes show promise but are not generally available and more information on specificity and cellular reactions is needed. We do not yet have probes that can quantify cellular production of specific oxidants. This article is part of a Special Issue entitled Current methods to study reactive oxygen species - pros and cons and biophysics of membrane proteins. Guest Editor: Christine Winterbourn. Copyright © 2013 Elsevier B.V. All rights reserved.

Effect of light on the kinetics and equilibrium of the textile dye (Reactive Red 120) adsorption by Helianthus annuus hairy roots.

PubMed

Srikantan, Chitra; Suraishkumar, G K; Srivastava, Smita

2018-06-01

The study demonstrates for the first time that light influences the adsorption equilibrium and kinetics of a dye by root culture system. The azo dye (Reactive Red 120) adsorption by the hairy roots of H. annuus followed a pseudo first-order kinetic model and the adsorption equilibrium parameters were best estimated using Langmuir isotherm. The maximum dye adsorption capacity of the roots increased 6-fold, from 0.26 mg g -1 under complete dark conditions to 1.51 mg g -1 under 16/8 h light/dark photoperiod. Similarly, adsorption rate of the dye and removal (%) also increased in the presence of light, irrespective of the initial concentration of the dye (20-110 mg L -1 ). The degradation of the azo dye upon adsorption by the hairy roots of H. annuus was also confirmed. In addition, a strategy for simultaneous dye removal and increased alpha-tocopherol (industrially relevant) production by H. annuus hairy root cultures has been proposed and demonstrated. Copyright © 2018 Elsevier Ltd. All rights reserved.

Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption.

NASA Astrophysics Data System (ADS)

Giannakoudakis, Dimitrios; Saroyan, Hayarpi; Lazaridis, Nikolaos; Deliyanni, Eleni

2016-04-01

Mesoporous magnetic activated carbon: Effect of preparation route on texture and surface properties and on effect for Reactive Black 5 adsorption. Dimitrios Giannakoudakis1, Hayarpi Saroyan2, Nikolaos Lazaridis2, Eleni Deliyanni2 1 City College of New York, Chemistry Department, 160 Convent Avenue, New York, United States 2 Laboratory of General and oInorganic Chemical Technology, Department of Chemistry, Aristotle University of Thessaloniki, GR-541 24 Thessaloniki, Greece In this study, the effect of preparation route of a mesoporous magnetic activated carbon on Reactive Black 5 (RB5) adsorption was investigated. The synthesis of the magnetic activated carbon was achieved both with (i) impregnation method (Bmi), and (ii) co-precipitation with two precipitation agents: NaOH (Bm) and NH4OH (Bma). After synthesis, the full characterization with various techniques (SEM, FTIR, XRD, DTA, DTG, VSM) was achieved in order to testify the effect of the preparation route on its textural and surface properties. It was shown that after the precipitation method the prepared carbon presented a collapsed texture and small magnetic properties. Effects of initial solution pH, effect of temperature, adsorption isotherms and kinetics were investigated in order to conclude about the aforementioned effect of the preparation method on dye adsorption performance of the magnetic carbons. The adsorption evaluation of the magnetic activated carbon presented higher adsorption capacity of Bmi carbon (350 mg/g) and lower of Bm (150 mg/g). Equilibrium experiments are also performed studying the effect of contact time (pseudo-first and -second order equations) and temperature (isotherms at 25, 45 and 65 °C fitted to Langmuir and Freundlich model). A full thermodynamic evaluation was carried out, calculating the parameters of enthalpy, free energy and entropy (ΔHο, ΔGο and ΔSο). The characterization with various techniques revealed the possible interactions/forces of dye-composite system.

Fluorescence probe techniques to monitor protein adsorption-induced conformation changes on biodegradable polymers.

PubMed

Benesch, Johan; Hungerford, Graham; Suhling, Klaus; Tregidgo, Carolyn; Mano, João F; Reis, Rui L

2007-08-15

The study of protein adsorption and any associated conformational changes on interaction with biomaterials is of great importance in the area of implants and tissue constructs. This study aimed to evaluate some fluorescent techniques to probe protein conformation on a selection of biodegradable polymers currently under investigation for biomedical applications. Because of the fluorescence emanating from the polymers, the use of monitoring intrinsic protein fluorescence was precluded. A highly solvatochromic fluorescent dye, Nile red, and a well-known protein label, fluorescein isothiocyanate, were employed to study the adsorption of serum albumin to polycaprolactone and to some extent also to two starch-containing polymer blends (SPCL and SEVA-C). A variety of fluorescence techniques, steady state, time resolved, and imaging were employed. Nile red was found to leach from the protein, while fluorescein isothiocyanate proved useful in elucidating a conformational change in the protein and the observation of protein aggregates adsorbed to the polymer surface. These effects were seen by making use of the phenomenon of energy migration between the fluorescent tags to monitor interprobe distance and the use of fluorescence lifetime imaging to ascertain the surface packing of the protein on polymer.

Enhanced reactive adsorption of hydrogen sulfide on the composites of graphene/graphite oxide with copper (hydr)oxychlorides.

PubMed

Mabayoje, Oluwaniyi; Seredych, Mykola; Bandosz, Teresa J

2012-06-27

Composites of copper (hydr)oxychlorides with graphite oxide or graphene were synthesized and used as adsorbents of hydrogen sulfide at dynamic conditions at ambient temperatures. The materials were extensively characterized before and after adsorption in order to link their performance to the surface features. X-ray diffraction, FTIR, thermal analysis, TEM, SEM/EDX, and adsorption of nitrogen were used. It was found that the composite with graphene has the most favorable surface features enhancing reactive adsorption of hydrogen sulfide. The presence of moisture in the H2S stream has a positive effect on the removal process owing to the dissociation process. H2S is retained on the surface via a direct replacement of OH groups and via acid-base reactions with the copper (hydr)oxide. Highly dispersed reduced copper species on the surface of the composite with graphene enhance activation of oxygen and cause formation of sulfites and sulfates. Higher conductivity of the graphene phase than that of graphite oxide helps in electron transfer in redox reactions.

AB INITIO Simulations of Desorption and Reactivity of Glycine at a Water-Pyrite Interface at ``Iron-Sulfur World'' Prebiotic Conditions

NASA Astrophysics Data System (ADS)

Pollet, Rodolphe; Boehme, Christian; Marx, Dominik

2006-08-01

Glycine at the interface of a pyrite surface (001) FeS2, and bulk water at high pressure and temperature conditions relevant to the “iron-sulfur world” scenario of the origin of life is investigated by theoretical means. Car-Parrinello molecular dynamics is used in order to study the desorption process of the zwitterionic form of this amino acid using two different adsorption modes, where either only one or both oxygens of the carboxylate group are anchored to surface iron atoms. It is found that the formation of stabilizing hydrogen bonds plays a key role in the detachment process, leading to longer retention times for the bidentate adsorption mode. In addition, the chemical reactivity of this heterogeneous system is probed by calculating the Fukui functions as site-specific reactivity indices. The most prominent targets for both nucleophilic and electrophilic reactions to occur are surface atoms, whereas the reactivity of glycine is only slightly affected upon anchoring.

Adaptive Neuro-Fuzzy Inference system analysis on adsorption studies of Reactive Red 198 from aqueous solution by SBA-15/CTAB composite

NASA Astrophysics Data System (ADS)

Aghajani, Khadijeh; Tayebi, Habib-Allah

2017-01-01

In this study, the Mesoporous material SBA-15 were synthesized and then, the surface was modified by the surfactant Cetyltrimethylammoniumbromide (CTAB). Finally, the obtained adsorbent was used in order to remove Reactive Red 198 (RR 198) from aqueous solution. Transmission electron microscope (TEM), Fourier transform infra-red spectroscopy (FTIR), Thermogravimetric analysis (TGA), X-ray diffraction (XRD), and BET were utilized for the purpose of examining the structural characteristics of obtained adsorbent. Parameters affecting the removal of RR 198 such as pH, the amount of adsorbent, and contact time were investigated at various temperatures and were also optimized. The obtained optimized condition is as follows: pH = 2, time = 60 min and adsorbent dose = 1 g/l. Moreover, a predictive model based on ANFIS for predicting the adsorption amount according to the input variables is presented. The presented model can be used for predicting the adsorption rate based on the input variables include temperature, pH, time, dosage, concentration. The error between actual and approximated output confirm the high accuracy of the proposed model in the prediction process. This fact results in cost reduction because prediction can be done without resorting to costly experimental efforts. SBA-15, CTAB, Reactive Red 198, adsorption study, Adaptive Neuro-Fuzzy Inference systems (ANFIS).

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE PAGES

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.; ...

2017-02-16

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular, with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry but are challenging to probe experimentally. Here, we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO 3 in humid conditions using ambient-pressure X-ray photoelectron spectroscopy. In comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO-terminated surface is more reactive toward water, forming hydroxyl species and adsorbing molecularmore » water at lower relative humidity than its FeO 2-terminated counterpart. But, the FeO 2-terminated surface forms more hydroxyl species during water adsorption at higher humidity, suggesting that adsorbate–adsorbate interactions may impact reactivity. These results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight that can aid in the design of catalyst materials.« less

Adsorption of 2-propanol on ice probed by ambient pressure X-ray photoelectron spectroscopy

DOE PAGES

Newberg, John T.; Bluhm, Hendrik

2015-08-18

The interaction of 2-propanol with ice was examined via ambient pressure X-ray photoelectron spectroscopy (APXPS), a surface sensitive technique that probes the adsorbed 2-propanol directly with submonolayer resolution. Isothermal uptake experiments were performed on vapor deposited ice at 227 K in the presence of the equilibrium water vapor pressure of 0.05 Torr and 2-propanol partial pressures ranging from 5 × 10 -5 to 2 × 10 -3 Torr. The C 1s APXPS spectra of adsorbed 2-propanol showed two characteristic peaks associated with the C OH alcohol group and C Me methyl groups in a 1 : 2 ratio, respectively. Coveragemore » increased with 2-propanol partial pressure and followed first order Langmuir kinetics with a Langmuir constant of K = 6.3 × 10 3 Torr -1. The 1 : 2 ratio of C OH : C Me remained constant with increasing coverage, indicating there is no chemical reaction upon adsorption. The observed Langmuir kinetics using APXPS is consistent with previous observations of other small chain alcohols via indirect adsorption methods using, e.g., Knudsen cell and coated wall flow tube reactors.« less

Elucidating the Structure-Reactivity Correlations of Phenothiazine-Based Fluorescent Probes toward ClO.

PubMed

Wang, Shichao; Zhang, Boyu; Wang, Wenjing; Feng, Gang; Yuan, Daqiang; Zhang, Xuanjun

2018-06-07

In this work, with the aim of developing effective molecular probes and investigating the structure-reactivity correlation, a short series of phenothiazine-based fluorescent probes are designed for the detection of ClO - with differing electron push-pull groups. Sensing experiment results and single-crystal X-ray analysis with the aid of time-dependent DFT (TD-DFT) calculations reveal that substituting groups with increasing electron-withdrawing ability can increase the dihedral angle of the phenothiazine moiety and reduce the gap energy of the probes, leading to enhanced reactivity toward ClO - . Both PT1 and PT2 show two-color switching upon detection of ClO - . PT1, with the strong electron-donating group thiophene, shows a fluorescence color switch from salmon to blue. PT2, with a medium electron-donating/accepting group benzothiazole, shows a fluorescence color switch from red to green. However, both PT1 and PT2 show almost no response to ONOO - . Through the introduction of strong electron-withdrawing ketone combined with a cyano group, PT3 shows a cyan emission upon detection of ClO - and weak red emission upon detection of ONOO - . HRMS and 1 H NMR results confirm that PT1 and PT2 have the same sensing mode, in which the divalent sulfur of phenothiazine can be oxidized to sulfoxide by ClO - . Upon reaction with ClO - , PT3 experiences two-step reactions. It is first oxidized into the sulfone structure by ClO - , and then transformed into sulfoxide phenothiazine aldehyde. Upon encountering ONOO - , PT3 changes into an aldehyde structure and some nonfluorescent byproducts. Owing to their special selectivity and high sensitivity, PT1 and PT2 are applied to image the endogenous ClO - in macrophage cells and zebrafish larvae. This study is expected to provide useful guidelines for probe design for various applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

PubMed Central

2015-01-01

Conspectus Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed “recognition” and “reactivity”. Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give

Adsorption of C.I. Reactive Red 228 and Congo Red dye from aqueous solution by amino-functionalized Fe3O4 particles: kinetics, equilibrium, and thermodynamics.

PubMed

Yan, Ting-guo; Wang, Li-Juan

2014-01-01

A magnetic adsorbent was synthesized by γ-aminopropyltriethoxysilane (APTES) modification of Fe(3)O(4) particles using a two-step process. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and vibration sample magnetometry were used to characterize the obtained magnetic adsorbent. EDS and XPS showed that APTES polymer was successfully introduced onto the as-prepared Fe(3)O(4)/APTES particle surfaces. The saturation magnetization of the magnetic adsorbent was around 65 emu g(-1), which indicated that the dye can be removed fast and efficiently from aqueous solution with an external magnetic field. The maximum adsorption capacities of Fe(3)O(4)/APTES for C.I. Reactive Red 228 (RR 228) and Congo Red (CR) were 51.4 and 118.8 mg g(-1), respectively. The adsorption of C.I. Reactive Red 228 (RR 228) and Congo Red (CR) on Fe(3)O(4)/APTES particles corresponded well to the Langmuir model and the Freundlich model, respectively. The adsorption processes for RR 228 and CR followed the pseudo-second-order model. The Boyd's film-diffusion model showed that film diffusion also played a major role in the studied adsorption processes for both dyes. Thermodynamic study indicated that both of the adsorption processes of the two dyes are spontaneous exothermic.

Electron Paramagnetic Resonance Measurements of Reactive Oxygen Species by Cyclic Hydroxylamine Spin Probes.

PubMed

Dikalov, Sergey I; Polienko, Yuliya F; Kirilyuk, Igor

2018-05-20

Oxidative stress contributes to numerous pathophysiological conditions such as development of cancer, neurodegenerative, and cardiovascular diseases. A variety of measurements of oxidative stress markers in biological systems have been developed; however, many of these methods are not specific, can produce artifacts, and do not directly detect the free radicals and reactive oxygen species (ROS) that cause oxidative stress. Electron paramagnetic resonance (EPR) is a unique tool that allows direct measurements of free radical species. Cyclic hydroxylamines are useful and convenient molecular probes that readily react with ROS to produce stable nitroxide radicals, which can be quantitatively measured by EPR. In this work, we critically review recent applications of various cyclic hydroxylamine spin probes in biology to study oxidative stress, their advantages, and the shortcomings. Recent Advances: In the past decade, a number of new cyclic hydroxylamine spin probes have been developed and their successful application for ROS measurement using EPR has been published. These new state-of-the-art methods provide improved selectivity and sensitivity for in vitro and in vivo studies. Although cyclic hydroxylamine spin probes EPR application has been previously described, there has been lack of translation of these new methods into biomedical research, limiting their widespread use. This work summarizes "best practice" in applications of cyclic hydroxylamine spin probes to assist with EPR studies of oxidative stress. Additional studies to advance hydroxylamine spin probes from the "basic science" to biomedical applications are needed and could lead to better understanding of pathological conditions associated with oxidative stress. Antioxid. Redox Signal. 28, 1433-1443.

New detection targets for amyloid-reactive probes: spectroscopic recognition of bacterial spores

NASA Astrophysics Data System (ADS)

Jones, Guilford, II; Landsman, Pavel

2005-05-01

We report characteristic changes in fluorescence of amyloid-binding dyes Thioflavin T (TfT), pinacyanol (PIN) and related dyes, caused by their interaction with suspended Bacillus spore cultures (B. subtilis, B thuringiensis). The gain in TfT emission in the presence of spores allowed their immediate detection in aqueous suspensions, with a sensitivity limit of < 105 spores per ml. The spectroscopic signatures are consistent with a large number of binding sites for the two dyes on spore coats. The possible structural relationship of these dye binding loci with characteristic motifs (β-stacks) of amyloid deposits and other misfolded protein formations suggests new designs for probing biocontamination and also for clinical studies of non-microbial human pathogens (e.g., amyloid-related protein aggregates in prion-related transmissible encephalopathies or in Alzheimer's disease). Also reported is a special screening technique that was designed and used herein for calibration of new detection probes and assays for spore detection. It employed spectroscopic interactions between the candidate amyloid stains and poly(vinylpyrrolidone)-coated colloid silica (Percoll) nanoparticles that also display remarkable parallelism with the corresponding dye-amyloid and dye-spore reactivities. Percoll may thus find new applications as a convenient non-biological structural model mimicking the putative probe-targeted motifs in both classes of bioanalytes. These findings are important in the design of new probes and assays for important human pathogens (i.e. bacterial spores and amyloidogenic protein aggregates).

Immobilization of ɛ-polylysine onto the probe surface for molecular adsorption type endotoxin detection system

NASA Astrophysics Data System (ADS)

Ooe, Katsutoshi; Tsuji, Akihito; Nishishita, Naoki; Hirano, Yoshiaki

2007-04-01

adsorption reaction between ɛ-polylysine and endotoxin. ɛ-polylysine has the structure of straight chain molecule composed by 25-30 residues made by lysine, and it is used as an antimicrobial agent, moreover, cellulose beads with immobilized ɛ-polylysine is used as the barrier filter for endotoxin removal. Therefore, it is expected that the endotoxin be adsorbed to the immobilized ɛ-polylysine onto the probe. As the result of this reaction, the mass of the probe is increased, and endotoxin can be detected by using of Quartz Crystal Microbalance (QCM). In our previous research, we have already acquired the proteins immobilization technique onto Au and Si surface. In this report, the proposal of molecular adsorption type endotoxin detection system, and the immobilization of ɛ-polylysine onto the probe are described. We use X-ray Photoelectron Spectroscopy (XPS) to confirm the ɛ-polylysine immobilization, and the adsorptive activity of immobilized ɛ-polylysine is measured by XPS and AFM. The purpose of this study is to bring about the realization of "Real-time endotoxin detection system".

Adsorption of reactive blue BF-5G dye by soybean hulls: kinetics, equilibrium and influencing factors.

PubMed

Honorio, Jacqueline Ferandin; Veit, Márcia Teresinha; Gonçalves, Gilberto da Cunha; de Campos, Élvio Antonio; Fagundes-Klen, Márcia Regina

2016-01-01

The textile industry is known for the high use of chemicals, such as dyes, and large volumes of effluent that contaminate waters, a fact that has encouraged research and improved treatment techniques. In this study, we used unprocessed soybean hulls for the removal of reactive blue BF-5G dye. The point of zero charge of soybean hulls was 6.76. Regarding the speed of agitation in the adsorption process, the resistance to mass transfer that occurs in the boundary layer was eliminated at 100 rpm. Kinetics showed an experimental amount of dye adsorbed at equilibrium of 57.473 mg g(-1) obtained under the following conditions: dye initial concentration = 400 mg L(-1); diameter of particle = 0.725 mm; dosage = 6 g L(-1); pH 2; 100 rpm; temperature = 30 °C; and duration of 24 hours. The pseudo-second order best showed the dye removal kinetics. The adsorption isotherms performed at different temperatures (20, 30, 40 and 50 °C) showed little variation in the concentration range assessed, being properly adjusted by the Langmuir isotherm model. The maximum capacity of dye adsorption was 72.427 mg g(-1) at 30 °C. Since soybean hull is a low-cost industrial byproduct, it proved to be a potential adsorbent for the removal of the textile dye assessed.

Goethite surface reactivity: III. Unifying arsenate adsorption behavior through a variable crystal face - Site density model

NASA Astrophysics Data System (ADS)

Salazar-Camacho, Carlos; Villalobos, Mario

2010-04-01

goethite, may be performed for each preparation either by experimental determination of site saturation by an index ion (e.g., chromate), or by achieving congruency of proton adsorption data with those of ideal goethites when plotted as percentage of proton-reactive ( lbond2 FeOH + lbond2 Fe 3OH) sites occupied. The surface arsenate complexes proposed additionally explained: (1) the higher affinity of goethite for As(V) than for Cr(VI) at high pH, and thus the gentle slope of the arsenate pH adsorption edges; and (2) the lower adsorption capacity for As(V) than for Cr(VI) at low pH on low-surface area goethites, through incomplete lbond2 FeOH site occupancy of As(V). The model is very promising as a practical means of predicting the adsorption behavior of arsenate on any goethite preparation, and may extend to predictive capabilities for adsorption behavior of many other relevant oxyanions, as well as for explaining differences in ligand-promoted surface transformation processes on goethite as a function of particle size.

Ozone adsorption on carbon nanoparticles

NASA Astrophysics Data System (ADS)

Chassard, Guillaume; Gosselin, Sylvie; Visez, Nicolas; Petitprez, Denis

2014-05-01

Carbonaceous particles produced by incomplete combustion or thermal decomposition of hydrocarbons are ubiquitous in the atmosphere. On these particles are adsorbed hundreds of chemical species. Those of great concern to health are polycyclic aromatic hydrocarbons (PAHs). During atmospheric transport, particulate PAHs react with gaseous oxidants. The induced chemical transformations may change toxicity and hygroscopicity of these potentially inhalable particles. The interaction between ozone and carbon particles has been extensively investigated in literature. However ozone adsorption and surface reaction mechanisms are still ambiguous. Some studies described a fast catalytic decomposition of ozone initiated by an atomic oxygen chemisorption followed by a molecular oxygen release [1-3]. Others suggested a reversible ozone adsorption according to Langmuir-type behaviour [4,5]. The aim of this present study is a better understanding of ozone interaction with carbon surfaces. An aerosol of carbon nanoparticles was generated by flowing synthetic air in a glass tube containing pure carbon (primary particles < 50 nm), under magnetic stirring. The aerosol was then mixed with ozone in an aerosol flow tube. Ozone uptake experiments were performed with different particles concentrations with a fixed ozone concentration. The influence of several factors on kinetics was examined: initial ozone concentration, particle size (50 nm ≤ Dp ≤ 200 nm) and competitive adsorption (with probe molecule and water). The effect of initial ozone concentration was first studied. Accordingly to literature, it has been observed that the number of gas-phase ozone molecules lost per unit particle surface area tends towards a plateau for high ozone concentration suggesting a reversible ozone adsorption according to a Langmuir mechanism. We calculated the initial reaction probability between O3 and carbon particles.An initial uptake coefficient of 1.10-4 was obtained. Similar experiments were

Physicochemical modeling of reactive violet 5 dye adsorption on home-made cocoa shell and commercial activated carbons using the statistical physics theory

NASA Astrophysics Data System (ADS)

Sellaoui, Lotfi; Lima, Éder Cláudio; Dotto, Guilherme Luiz; Dias, Silvio L. P.; Ben Lamine, Abdelmottaleb

Two equilibrium models based on statistical physics, i.e., monolayer model with single energy and multilayer model with saturation, were developed and employed to access the steric and energetic aspects in the adsorption of reactive violet 5 dye (RV-5) on cocoa shell activated carbon (AC) and commercial activated carbon (CAC), at different temperatures (from 298 to 323 K). The results showed that the multilayer model with saturation was able to represent the adsorption system. This model assumes that the adsorption occurs by a formation of certain number of layers. The n values ranged from 1.10 to 2.98, indicating that the adsorbate molecules interacted in an inclined position on the adsorbent surface and aggregate in solution. The study of the total number of the formed layers (1 + L2) showed that the steric hindrance is the dominant factor. The description of the adsorbate-adsorbent interactions by calculation of the adsorption energy indicated that the process occurred by physisorption in nature, since the values were lower than 40 kJ mol-1.

Adsorption, Ordering, and Local Environments of Surfactant-Encapsulated Polyoxometalate Ions Probed at the Air–Water Interface

DOE PAGES

Doughty, Benjamin; Yin, Panchao; Ma, Ying-Zhong

2016-07-23

The continued development and application of surfactant-encapsulated polyoxometalates (SEPs) relies on understanding the ordering and organization of species at their interface and how these are impacted by the various local environments to which they are exposed. In this paper, we report on the equilibrium properties of two common SEPs adsorbed to the air–water interface and probed with surface-specific vibrational sum-frequency generation (SFG) spectroscopy. These results reveal clear shifts in vibrational band positions, the magnitude of which scales with the charge of the SEP core, which is indicative of a static field effect on the surfactant coating and the associated localmore » chemical environment. This static field also induces ordering in surrounding water molecules that is mediated by charge screening via the surface-bound surfactants. From these SFG measurements, we are able to show that Mo 132-based SEPs are more polar than Mo 72V 30 SEPs. Disorder in the surfactant chain packing at the highly curved SEP surfaces is attributed to large conic volumes that can be sampled without interactions with neighboring chains. Measurements of adsorption isotherms yield free energies of adsorption to the air–water interface of -46.8 ± 0.4 and -44.8 ± 1.2 kJ/mol for the Mo 132 and Mo 72V 30 SEPs, respectively, indicating a strong propensity for the fluid surface. Finally, the influence of intermolecular interactions on the surface adsorption energies is discussed.« less

Using the Multipole Resonance Probe to Stabilize the Electron Density During a Reactive Sputter Process

NASA Astrophysics Data System (ADS)

Oberberg, Moritz; Styrnoll, Tim; Ries, Stefan; Bienholz, Stefan; Awakowicz, Peter

2015-09-01

Reactive sputter processes are used for the deposition of hard, wear-resistant and non-corrosive ceramic layers such as aluminum oxide (Al2O3) . A well known problem is target poisoning at high reactive gas flows, which results from the reaction of the reactive gas with the metal target. Consequently, the sputter rate decreases and secondary electron emission increases. Both parameters show a non-linear hysteresis behavior as a function of the reactive gas flow and this leads to process instabilities. This work presents a new control method of Al2O3 deposition in a multiple frequency CCP (MFCCP) based on plasma parameters. Until today, process controls use parameters such as spectral line intensities of sputtered metal as an indicator for the sputter rate. A coupling between plasma and substrate is not considered. The control system in this work uses a new plasma diagnostic method: The multipole resonance probe (MRP) measures plasma parameters such as electron density by analyzing a typical resonance frequency of the system response. This concept combines target processes and plasma effects and directly controls the sputter source instead of the resulting target parameters.

Detection of reactive oxygen species in mainstream cigarette smoke by a fluorescent probe

NASA Astrophysics Data System (ADS)

Liu, Li; Xu, Shi-jie; Li, Song-zhan

2009-07-01

A mass of reactive oxygen species(ROS) are produced in the process of smoking. Superfluous ROS can induce the oxidative stress in organism, which will cause irreversible damage to cells. Fluorescent probe is taken as a marker of oxidative stress in biology and has been applied to ROS detection in the field of biology and chemistry for high sensitivity, high simplicity of data collection and high resolution. As one type of fluorescent probe, dihydrorhodamine 6G (dR6G) will be oxidized to the fluorescent rhodamine 6G, which could be used to detect ROS in mainstream cigarette smoke. We investigated the action mechanism of ROS on dR6G, built up the standard curve of R6G fluorescence intensity with its content, achieved the variation pattern of R6G fluorescence intensity with ROS content in mainstream cigarette smoke and detected the contents of ROS from the 4 types of cigarettes purchased in market. The result shows that the amount of ROS has close relationship with the types of tobacco and cigarette production technology. Compared with other detecting methods such as electronic spin resonance(ESR), chromatography and mass spectrometry, this detection method by the fluorescent probe has higher efficiency and sensitivity and will have wide applications in the ROS detection field.

Adsorption of arsenic(III) into modified lamellar Na-magadiite in aqueous medium-Thermodynamic of adsorption process

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lima Guerra, Denis; Azevedo Pinto, Alane; Airoldi, Claudio

2008-12-15

Synthetic Na-magadiite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide, after expanding the interlayer distance with polar organic solvents such as dimethylsulfoxide (DMSO). The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298{+-}1 K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression nonlinear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic ({delta}{sub int}H=-4.15-5.98 kJ mol{sup -1}) accompanied by increase in entropy ({delta}{sub int}S=41.32-62.20 J k{sup -1} mol{sup -1}) and Gibbs energy ({delta}{sub int}G=-22.44-24.56 kJmore » mol{sup -1}). The favorable values corroborate with the arsenic (III)/basic reactive centers interaction at the solid-liquid interface in the spontaneous process. - Grapical Abstract: The results suggest that the adsorption capacities increased with an increase of reactive basic centers in the pendant organic chains of the intercalated agent.« less

Chemical sensors based on N-substituted polyaniline derivatives: reactivity and adsorption studies via electronic structure calculations.

PubMed

Mandú, Larissa O; Batagin-Neto, Augusto

2018-06-09

Conjugated organic polymers represent an important class of materials for varied technological applications including in active layers of chemical sensors. In this context, polyaniline (PANI) derivatives are promising candidates, mainly due to their high chemical stability, good processability, versatility of synthesis, polymerization, and doping, as well as relative low cost. In this study, electronic structure calculations were carried out for varied N-substituted PANI derivatives in order to investigate the potential sensory properties of these materials. The opto-electronic properties of nine distinct compounds were evaluated and discussed in terms of the employed substituents. Preliminary reactivity studies were performed in order to identify adsorption centers on the oligomer structures via condensed-to-atoms Fukui indexes (CAFI). Finally, adsorption studies were carried out for selected derivatives considering five distinct gaseous analytes. The influence of the analytes on the oligomer properties were investigated via the evaluation of average binding energies and changes on the structural features, optical absorption spectra, frontier orbitals distribution, and total density of states in relation to the isolated oligomers. The obtained results indicate the derivatives PANI-NO 2 and PANI-C 6 H 5 as promising materials for the development of improved chemical sensors.

Preparation of Chitosan Coated Magnetic Hydroxyapatite Nanoparticles and Application for Adsorption of Reactive Blue 19 and Ni2+ Ions

PubMed Central

Nguyen, Van Cuong; Pho, Quoc Hue

2014-01-01

An adsorbent called chitosan coated magnetic hydroxyapatite nanoparticles (CS-MHAP) was prepared with the purpose of improvement for the removal of Ni2+ ions and textile dye by coprecipitation. Structure and properties of CS-MHAP were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and vibrating sample magnetometer (VSM). Weight percent of chitosan was investigated by thermal gravimetric analysis (TGA). The prepared CS-MHAP presents a significant improvement on the removal efficiency of Ni2+ ions and reactive blue 19 dye (RB19) in comparison with chitosan and magnetic hydroxyapatite nanoparticles. Moreover, the adsorption capacities were affected by several parameters such as contact time, initial concentration, adsorbent dosage, and initial pH. Interestingly, the prepared adsorbent could be easily recycled from an aqueous solution by an external magnet and reused for adsorption with high removal efficiency. PMID:24592158

Chemical Probes for Molecular Imaging and Detection of Hydrogen Sulfide and Reactive Sulfur Species in Biological Systems

PubMed Central

2014-01-01

Hydrogen sulfide (H2S), a gaseous species produced by both bacteria and higher eukaryotic organisms, including mammalian vertebrates, has attracted attention in recent years for its contributions to human health and disease. H2S has been proposed as a cytoprotectant and gasotransmitter in many tissue types, including mediating vascular tone in blood vessels as well as neuromodulation in the brain. The molecular mechanisms dictating how H2S affects cellular signaling and other physiological events remain insufficiently understood. Furthermore, the involvement of H2S in metal-binding interactions and formation of related RSS such as sulfane sulfur may contribute to other distinct signaling pathways. Owing to its widespread biological roles and unique chemical properties, H2S is an appealing target for chemical biology approaches to elucidate its production, trafficking, and downstream function. In this context, reaction-based fluorescent probes offer a versatile set of screening tools to visualize H2S pools in living systems. Three main strategies used in molecular probe development for H2S detection include azide and nitro group reduction, nucleophilic attack, and CuS precipitation. Each of these approaches exploit the strong nucleophilicity and reducing potency of H2S to achieve selectivity over other biothiols. In addition, a variety of methods have been developed for the detection of other reactive sulfur species (RSS), including sulfite and bisulfite, as well as sulfane sulfur species and related modifications such as S-nitrosothiols. Access to this growing chemical toolbox of new molecular probes for H2S and related RSS sets the stage for applying these developing technologies to probe reactive sulfur biology in living systems. PMID:25474627

The Importance of Protons in Reactive Transport Modeling

NASA Astrophysics Data System (ADS)

McNeece, C. J.; Hesse, M. A.

2014-12-01

The importance of pH in aqueous chemistry is evident; yet, its role in reactive transport is complex. Consider a column flow experiment through silica glass beads. Take the column to be saturated and flowing with solution of a distinct pH. An instantaneous change in the influent solution pH can yield a breakthrough curve with both a rarefaction and shock component (composite wave). This behavior is unique among aqueous ions in transport and is more complex than intuition would tell. Analysis of the hyperbolic limit of this physical system can explain these first order transport phenomenon. This analysis shows that transport behavior is heavily dependent on the shape of the adsorption isotherm. Hence it is clear that accurate surface chemistry models are important in reactive transport. The proton adsorption isotherm has nonconstant concavity due to the proton's ability to partition into hydroxide. An eigenvalue analysis shows that an inflection point in the adsorption isotherm allows the development of composite waves. We use electrostatic surface complexation models to calculate realistic proton adsorption isotherms. Surface characteristics such as specific surface area, and surface site density were determined experimentally. We validate the model by comparison against silica glass bead flow through experiments. When coupled to surface complexation models, the transport equation captures the timing and behavior of breakthrough curves markedly better than with commonly used Langmuir assumptions. Furthermore, we use the adsorption isotherm to predict, a priori, the transport behavior of protons across pH composition space. Expansion of the model to multicomponent systems shows that proton adsorption can force composite waves to develop in the breakthrough curves of ions that would not otherwise exhibit such behavior. Given the abundance of reactive surfaces in nature and the nonlinearity of chemical systems, we conclude that building a greater understanding of

THE INTEGRATED USE OF COMPUTATIONAL CHEMISTRY, SCANNING PROBE MICROSCOPY, AND VIRTUAL REALITY TO PREDICT THE CHEMICAL REACTIVITY OF ENVIRONMENTAL SURFACES

EPA Science Inventory

In the last decade three new techniques scanning probe microscopy (SPM), virtual reality (YR) and computational chemistry ave emerged with the combined capability of a priori predicting the chemically reactivity of environmental surfaces. Computational chemistry provides the cap...

Adsorption of a cationic dye molecule on polystyrene microspheres in colloids: effect of surface charge and composition probed by second harmonic generation.

PubMed

Eckenrode, Heather M; Jen, Shih-Hui; Han, Jun; Yeh, An-Gong; Dai, Hai-Lung

2005-03-17

Nonlinear optical probe, second harmonic generation (SHG), of the adsorption of the dye molecule malachite green (MG), in cationic form at pH < or = 5, on polystyrene microspheres in aqueous solution is used to study the effect of surface charge and composition on molecular adsorption. Three types of polystyrene microspheres with different surface composition are investigated: (1) a sulfate terminated, anionic surface, (2) a neutral surface without any functional group termination, and (3) an amine terminated, cationic surface. The cationic dye was found to adsorb at all three surfaces, regardless of surface charge. The adsorption free energies, DeltaG's, measured for the three surfaces are -12.67, -12.39, and -10.46 kcal/mol, respectively, with the trend as expected from the charge interactions. The adsorption density on the anionic surface, where attractive charge-charge interaction dominates, is determined by the surface negative charge density. The adsorption densities on the neutral and cationic surfaces are on the other hand higher, perhaps as a result of a balance between minimizing repulsive charge interaction and maximizing attractive molecule-substrate and intermolecular interactions. The relative strength of the SH intensity per molecule, in combination of a model calculation, reveals that the C(2) axis of the MG molecule is nearly perpendicular to the surface on the anionic surface and tilts away from the surface norm when the surface is neutral and further away when cationic. Changing the pH of the solution may alter the surface charge and subsequently affect the adsorption configuration and SH intensity.

Reactive adsorption of SO2 on activated carbons with deposited iron nanoparticles.

PubMed

Arcibar-Orozco, Javier A; Rangel-Mendez, J Rene; Bandosz, Teresa J

2013-02-15

The effect of iron particle size anchored on the surface of commercial activated carbon on the removal of SO(2) from a gas phase was studied. Nanosize iron particles were deposited using forced hydrolysis of FeCl(3) with or without H(3)PO(4) as a capping agent. Dynamic adsorption experiments were carried out on either dry or pre-humidified materials and the adsorption capacities were calculated. The surface of the initial and exhausted materials was extensively characterized by microscopic, porosity, thermogravimetric and surface chemistry. The results indicate that the SO(2) adsorption capacity increased two and half times after the prehumidification process owing to the formation of H(2)SO(4) in the porous system. Iron species enhance the SO(2) adsorption capacity only when very small nanoparticles are deposited on the pore walls as a thin layer. Large iron nanoparticles block the ultramicropores decreasing the accessibility of the active sites and consuming oxygen that rest adsorption centers for SO(2) molecules. Iron nanoparticles of about 3-4 nm provide highly dispersed adsorption sites for SO(2) molecules and thus increase the adsorption capacity of about 80%. Fe(2)(SO(4))(3) was detected on the surface of exhausted samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite.

PubMed

Al-Ghouti, Mohammad A; Al-Degs, Yehya S; Khraisheh, Majeda A M; Ahmad, Mohammad N; Allen, Stephen J

2009-08-01

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.

Selective adsorption of toluene-3,4-dithiol on Si(553)-Au surfaces

NASA Astrophysics Data System (ADS)

Suchkova, Svetlana; Hogan, Conor; Bechstedt, Friedhelm; Speiser, Eugen; Esser, Norbert

2018-01-01

The adsorption of small organic molecules onto vicinal Au-stabilized Si(111) surfaces is shown to be a versatile route towards controlled growth of ordered organic-metal hybrid one-dimensional nanostructures. Density functional theory is used to investigate the site-specific adsorption of toluene-3,4-dithiol (TDT) molecules onto the clean Si(553)-Au surface and onto a co-doped surface whose steps are passivated by hydrogen. We find that the most reactive sites involve bonding to silicon at the step edge or on the terraces, while gold sites are relatively unfavored. H passivation and TDT adsorption both induce a controlled charge redistribution within the surface layer, causing the surface metallicity, electronic structure, and chemical reactivity of individual adsorption sites to be substantially altered.

Recent Progress in Fluorescent Imaging Probes

PubMed Central

Pak, Yen Leng; Swamy, K. M. K.; Yoon, Juyoung

2015-01-01

Due to the simplicity and low detection limit, especially the bioimaging ability for cells, fluorescence probes serve as unique detection methods. With the aid of molecular recognition and specific organic reactions, research on fluorescent imaging probes has blossomed during the last decade. Especially, reaction based fluorescent probes have been proven to be highly selective for specific analytes. This review highlights our recent progress on fluorescent imaging probes for biologically important species, such as biothiols, reactive oxygen species, reactive nitrogen species, metal ions including Zn2+, Hg2+, Cu2+ and Au3+, and anions including cyanide and adenosine triphosphate (ATP). PMID:26402684

Recent Progress in Fluorescent Imaging Probes.

PubMed

Pak, Yen Leng; Swamy, K M K; Yoon, Juyoung

2015-09-22

Due to the simplicity and low detection limit, especially the bioimaging ability for cells, fluorescence probes serve as unique detection methods. With the aid of molecular recognition and specific organic reactions, research on fluorescent imaging probes has blossomed during the last decade. Especially, reaction based fluorescent probes have been proven to be highly selective for specific analytes. This review highlights our recent progress on fluorescent imaging probes for biologically important species, such as biothiols, reactive oxygen species, reactive nitrogen species, metal ions including Zn(2+), Hg(2+), Cu(2+) and Au(3+), and anions including cyanide and adenosine triphosphate (ATP).

Water adsorption on TiO2 surfaces probed by soft X-ray spectroscopies: bulk materials vs. isolated nanoparticles

PubMed Central

Benkoula, Safia; Sublemontier, Olivier; Patanen, Minna; Nicolas, Christophe; Sirotti, Fausto; Naitabdi, Ahmed; Gaie-Levrel, François; Antonsson, Egill; Aureau, Damien; Ouf, François-Xavier; Wada, Shin-Ichi; Etcheberry, Arnaud; Ueda, Kiyoshi; Miron, Catalin

2015-01-01

We describe an experimental method to probe the adsorption of water at the surface of isolated, substrate-free TiO2 nanoparticles (NPs) based on soft X-ray spectroscopy in the gas phase using synchrotron radiation. To understand the interfacial properties between water and TiO2 surface, a water shell was adsorbed at the surface of TiO2 NPs. We used two different ways to control the hydration level of the NPs: in the first scheme, initially solvated NPs were dried and in the second one, dry NPs generated thanks to a commercial aerosol generator were exposed to water vapor. XPS was used to identify the signature of the water layer shell on the surface of the free TiO2 NPs and made it possible to follow the evolution of their hydration state. The results obtained allow the establishment of a qualitative determination of isolated NPs’ surface states, as well as to unravel water adsorption mechanisms. This method appears to be a unique approach to investigate the interface between an isolated nano-object and a solvent over-layer, paving the way towards new investigation methods in heterogeneous catalysis on nanomaterials. PMID:26462615

Adsorption of n-butane on graphene/Ru(0001)—A molecular beam scattering study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sivapragasam, Nilushni; Nayakasinghe, Mindika T.; Burghaus, Uwe, E-mail: uwe.burghaus@ndsu.edu

2016-07-15

Adsorption kinetics/dynamics of n-butane on graphene, physical vapor deposited on Ru(0001) (hereafter G/Ru), and bare Ru(0001) (hereafter Ru) are discussed. The chemical activity of the supported-graphene as well as the support was probed by thermal desorption spectroscopy (adsorption kinetics). In addition and to the best of our knowledge, for the first time, molecular beam scattering data of larger molecules were collected for graphene (probing the adsorption dynamics). Furthermore, samples were inspected by x-ray photoelectron spectroscopy and Auger electron spectroscopy. At the measuring conditions used here, n-butane adsorption kinetics/dynamics are molecular and nonactivated. Binding energies of butane on Ru and G/Rumore » are indistinguishable within experimental uncertainty. Thus, G/Ru is “kinetically transparent.” Initial adsorption probabilities, S{sub 0}, of n-butane decrease with increasing impact energy (0.76–1.72 eV) and are adsorption temperature independent for both Ru and G/Ru, again consistent with molecular adsorption. Also, S{sub 0} of Ru and G/Ru are indistinguishable within experimental uncertainty. Thus, G/Ru is “dynamically transparent.” Coverage dependent adsorption probabilities indicate precursor effects for graphene/Ru.« less

Surface-enhanced Raman scattering (SERS) dosimeter and probe

DOEpatents

Vo-Dinh, Tuan

1995-01-01

A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devises, in probe array devices.

Adsorption with biodegradation for decolorization of reactive black 5 by Funalia trogii 200800 on a fly ash-chitosan medium in a fluidized bed bioreactor-kinetic model and reactor performance.

PubMed

Lin, Yen-Hui; Lin, Wen-Fan; Jhang, Kai-Ning; Lin, Pei-Yu; Lee, Mong-Chuan

2013-02-01

A non-steady-state mathematical model system for the kinetics of adsorption and biodegradation of reactive black 5 (RB5) by Funalia trogii (F. trogii) ATCC 200800 biofilm on fly ash-chitosan bead in the fluidized bed process was derived. The mechanisms in the model system included adsorption by fly ash-chitosan beads, biodegradation by F. trogii cells and mass transport diffusion. Batch kinetic tests were independently performed to determine surface diffusivity of RB5, adsorption parameters for RB5 and biokinetic parameters of F. trogii ATCC 200800. A column test was conducted using a continuous-flow fluidized bed reactor with a recycling pump to approximate a completely-mixed flow reactor for model verification. The experimental results indicated that F. trogii biofilm bioregenerated the fly ash-chitosan beads after attached F. trogii has grown significantly. The removal efficiency of RB5 was about 95 % when RB5 concentration in the effluent was approximately 0.34 mg/L at a steady-state condition. The concentration of suspended F. trogii cells reached up to about 1.74 mg/L while the thickness of attached F. trogii cells was estimated to be 80 μm at a steady-state condition by model prediction. The comparisons of experimental data and model prediction show that the model system for adsorption and biodegradation of RB5 can predict the experimental results well. The approaches of experiments and mathematical modeling in this study can be applied to design a full-scale fluidized bed process to treat reactive dye in textile wastewater.

Surface-enhanced Raman scattering (SERS) dosimeter and probe

DOEpatents

Vo-Dinh, T.

1995-03-21

A dosimeter and probe for measuring exposure to chemical and biological compounds is disclosed. The dosimeter or probe includes a collector which may be analyzed by surface-enhanced Raman spectroscopy. The collector comprises a surface-enhanced Raman scattering-active material having a coating applied thereto to improve the adsorption properties of the collector. The collector may also be used in automated sequential devices, in probe array devices. 10 figures.

SERS-activating effect of chlorides on borate-stabilized silver nanoparticles: formation of new reduced adsorption sites and induced nanoparticle fusion.

PubMed

Sloufová, Ivana; Sisková, Karolína; Vlcková, Blanka; Stepánek, Josef

2008-04-28

Changes in morphology, surface reactivity and surface-enhancement of Raman scattering induced by modification of borate-stabilized Ag nanoparticles by adsorbed chlorides have been explored using TEM, EDX analysis and SERS spectra of probing adsorbate 2,2'-bipyridine (bpy) excited at 514.5 nm and evaluated by factor analysis. At fractional coverages of the parent Ag nanoparticles by adsorbed chlorides <0.6, the Ag colloid/Cl(-)/bpy systems were found to be constituted by fractal aggregates of Ag nanoparticles fairly uniform in size (10 +/- 2 nm) and SERS spectra of Ag(+)-bpy surface species were detected. The latter result was interpreted in terms of the presence of oxidized Ag(+) and/or Ag(n)(+) adsorption sites, which have been encountered also in systems with the chemically untreated Ag nanoparticles. At chloride coverages >0.6, a fusion of fractal aggregates into the compact aggregates of touching and/or interpenetrating Ag nanoparticles has been observed and found to be accompanied by the formation of another surface species, Ag-bpy, as well as by the increase of the overall SERS enhancement of bpy by factor of 40. The same Ag-bpy surface species has been detected under the strongly reducing conditions of reduction of silver nitrate by sodium borohydride in the presence of bpy. The formation of Ag-bpy is thus interpreted in terms of the stabilization of reduced Ag(0) adsorption sites by adsorbed bpy. The formation of reduced adsorption sites on Ag nanoparticle surfaces at chloride coverages >0.6 is discussed in terms of local changes in the work function of Ag. Finally, the SERS spectral detection of Ag-bpy species is proposed as a tool for probing the presence of reduced Ag(0) adsorption sites in systems with chemically modified Ag nanoparticles.

Adsorption and decomposition of dimethyl methylphosphonate (DMMP) on expanded graphite/metal oxides

NASA Astrophysics Data System (ADS)

Hung, Wei-Che; Wang, Je-Chuang; Wu, Kuo-Hui

2018-06-01

Composites based on expanded graphite (EG) and metal oxides (MOs) were prepared by an explosive combustion and blending method. A metal oxide (Ag2O, CuO or ZnO)-containing phase was employed as a component with reactive functionality, which was supported on EG as a component with adsorptive functionality. The physical properties of the EG/MO composites were examined using SEM and FTIR spectroscopy, the results of which indicated that the MOs were incorporated in the EG matrix after impregnation. Solid state magic angle spinning (MAS) 1H, 31P and cross polarization (CP) MAS 13C NMR studies of the EG/MO composites were performed after adsorption of dimethyl methylphosphonate (DMMP). The FTIR and NMR data showed that the initial uptake occurred through both molecular and reactive adsorption. Molecular adsorption occurred by van der Waals interaction of M(Zn, Cu, Ag)⋯Odbnd P and hydrogen-bond formation to isolated hydroxyl groups. Reactive chemisorption appeared to occur through interaction with both Lewis acid sites and active oxygen species present on the MO surface. The FTIR and NMR results exhibited a trend of reactivity towards DMMP in the order Ag2O > ZnO > CuO, which indicated stronger interaction between the Lewis acid sites and the phosphoryl O atom of DMMP for Ag2O as compared with ZnO and CuO, with concomitant formation of surface-coordinated DMMP and bridge-bonded Osbnd Psbnd O phosphorus oxide species.

Activatable fluorescent probes in fluorescence-guided surgery: Practical considerations.

PubMed

Mochida, Ai; Ogata, Fusa; Nagaya, Tadanobu; Choyke, Peter L; Kobayashi, Hisataka

2018-02-15

Fluorescence-guided imaging during surgery is a promising technique that is increasingly used to aid surgeons in identifying sites of tumor and surgical margins. Of the two types of fluorescent probes, always-on and activatable, activatable probes are preferred because they produce higher target-to-background ratios, thus improving sensitivity compared with always-on probes that must contend with considerable background signal. There are two types of activatable probes: 1) enzyme-reactive probes that are normally quenched but can be activated after cleavage by cancer-specific enzymes (activity-based probes) and 2) molecular-binding probes which use cancer targeting moieties such as monoclonal antibodies to target receptors found in abundance on cancers and are activated after internalization and lysosomal processing (binding-based probes). For fluorescence-guided intraoperative surgery, enzyme-reactive probes are superior because they can react quickly, require smaller dosages especially for topical applications, have limited side effects, and have favorable pharmacokinetics. Enzyme-reactive probes are easier to use, fit better into existing work flows in the operating room and have minimal toxicity. Although difficult to prove, it is assumed that the guidance provided to surgeons by these probes results in more effective surgeries with better outcomes for patients. In this review, we compare these two types of activatable fluorescent probes for their ease of use and efficacy. Published by Elsevier Ltd.

Environmental applications using graphene composites: water remediation and gas adsorption.

PubMed

Kemp, K Christian; Seema, Humaira; Saleh, Muhammad; Le, Nhien H; Mahesh, Kandula; Chandra, Vimlesh; Kim, Kwang S

2013-04-21

This review deals with wide-ranging environmental studies of graphene-based materials on the adsorption of hazardous materials and photocatalytic degradation of pollutants for water remediation and the physisorption, chemisorption, reactive adsorption, and separation for gas storage. The environmental and biological toxicity of graphene, which is an important issue if graphene composites are to be applied in environmental remediation, is also addressed.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

2014-04-29

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D; Sulchek, Todd A; Feigin, Stuart C

2013-04-30

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D [Reno, NV; Sulchek, Todd A [Oakland, CA; Feigin, Stuart C [Reno, NV

2012-07-10

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

Cantilevered probe detector with piezoelectric element

DOEpatents

Adams, Jesse D.; Sulchek, Todd A.; Feigin, Stuart C.

2010-04-06

A disclosed chemical detection system for detecting a target material, such as an explosive material, can include a cantilevered probe, a probe heater coupled to the cantilevered probe, and a piezoelectric element disposed on the cantilevered probe. The piezoelectric element can be configured as a detector and/or an actuator. Detection can include, for example, detecting a movement of the cantilevered probe or a property of the cantilevered probe. The movement or a change in the property of the cantilevered probe can occur, for example, by adsorption of the target material, desorption of the target material, reaction of the target material and/or phase change of the target material. Examples of detectable movements and properties include temperature shifts, impedance shifts, and resonant frequency shifts of the cantilevered probe. The overall chemical detection system can be incorporated, for example, into a handheld explosive material detection system.

A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts

NASA Astrophysics Data System (ADS)

Cybulskis, Viktor J.; Harris, James W.; Zvinevich, Yury; Ribeiro, Fabio H.; Gounder, Rajamani

2016-10-01

A design is presented for a versatile transmission infrared cell that can interface with an external vacuum manifold to undergo in situ gas treatments and receive controlled doses of various adsorbates and probe molecules, allowing characterization of heterogeneous catalyst surfaces in order to identify and quantify active sites and adsorbed surface species. Critical design characteristics include customized temperature control for operation between cryogenic and elevated temperatures (100-1000 K) and modified Cajon fittings for operation over a wide pressure range (10-2-103 Torr) that eliminates the complications introduced when using sealants or flanges to secure cell windows. The customized, hand-tightened Cajon fittings simplify operation of the cell compared to previously reported designs, because they allow for rapid cell assembly and disassembly and, in turn, replacement of catalyst samples. In order to validate the performance of the cell, transmission infrared spectroscopic experiments are reported to characterize the Brønsted and Lewis acid sites present in H-beta and H-mordenite zeolites using cryogenic adsorption of CO (<150 K).

A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts.

PubMed

Cybulskis, Viktor J; Harris, James W; Zvinevich, Yury; Ribeiro, Fabio H; Gounder, Rajamani

2016-10-01

A design is presented for a versatile transmission infrared cell that can interface with an external vacuum manifold to undergo in situ gas treatments and receive controlled doses of various adsorbates and probe molecules, allowing characterization of heterogeneous catalyst surfaces in order to identify and quantify active sites and adsorbed surface species. Critical design characteristics include customized temperature control for operation between cryogenic and elevated temperatures (100-1000 K) and modified Cajon fittings for operation over a wide pressure range (10 -2 -10 3 Torr) that eliminates the complications introduced when using sealants or flanges to secure cell windows. The customized, hand-tightened Cajon fittings simplify operation of the cell compared to previously reported designs, because they allow for rapid cell assembly and disassembly and, in turn, replacement of catalyst samples. In order to validate the performance of the cell, transmission infrared spectroscopic experiments are reported to characterize the Brønsted and Lewis acid sites present in H-beta and H-mordenite zeolites using cryogenic adsorption of CO (<150 K).

Problems affecting the fidelity of pressure measuring instruments for planetary probes

NASA Technical Reports Server (NTRS)

Hudson, J. B.

1972-01-01

Determination is made of the nature and magnitude of surface-related effects that cause errors in pressure measuring instruments, with special reference being made to instruments intended for use in planetary probes. The interaction of gases with clean surfaces of metals likely to be used as gage construction materials was studied. Special emphasis was placed on the adsorption, chemical reaction, and electron-induced desorption processes. The results indicated that all metals tested were subject to surface processes which would degrade gage fidelity. It was also found, however, that the formation of inert adsorbed layers on these metal surfaces, such as carbon on platinum, greatly reduced or eliminated these effects. This process, combined with a system design which avoids contact between reactive gases and hot filaments, appears to offer the most promising solution to the gage fidelity problem.

Probing Gas Adsorption in Zeolites by Variable-Temperature IR Spectroscopy: An Overview of Current Research.

PubMed

Garrone, Edoardo; Delgado, Montserrat R; Bonelli, Barbara; Arean, Carlos O

2017-09-15

The current state of the art in the application of variable-temperature IR (VTIR) spectroscopy to the study of (i) adsorption sites in zeolites, including dual cation sites; (ii) the structure of adsorption complexes and (iii) gas-solid interaction energy is reviewed. The main focus is placed on the potential use of zeolites for gas separation, purification and transport, but possible extension to the field of heterogeneous catalysis is also envisaged. A critical comparison with classical IR spectroscopy and adsorption calorimetry shows that the main merits of VTIR spectroscopy are (i) its ability to provide simultaneously the spectroscopic signature of the adsorption complex and the standard enthalpy change involved in the adsorption process; and (ii) the enhanced potential of VTIR to be site specific in favorable cases.

Using chromate to investigate the impact of natural organics on the surface reactivity of nanoparticulate magnetite

USGS Publications Warehouse

Swindle, Andrew L.; Cozzarelli, Isabelle M.; Elwood Madden, Andrew S.

2015-01-01

Chromate was used as a chemical probe to investigate the size-dependent influence of organics on nanoparticle surface reactivity. Magnetite–chromate sorption experiments were conducted with ∼90 and ∼6 nm magnetite nanoparticles in the presence and absence of fulvic acid (FA), natural organic matter (NOM), and isolated landfill leachate (LL). Results indicated that low concentrations (1 mg/L) of organics had no noticeable impact on chromate sorption, whereas concentrations of 50 mg/L or more resulted in decreased amounts of chromate sorption. The adsorption of organics onto the magnetite surfaces interfered equally with the ability of the 6 and 90 nm particles to sorb chromate from solution, despite the greater surface area of the smaller particles. Results indicate the presence of organics did not impact the redox chemistry of the magnetite–chromate system over the duration of the experiments (8 h), nor did the organics interact with the chromate in solution. Brunauer–Emmett–Teller (BET) and scanning electron microscopy (SEM) results indicate that the organics blocked the surface reactivity by occupying surface sites on the particles. The similarity of results with FA and NOM suggests that coverage of the reactive mineral surface is the main factor behind the inhibition of surface reactivity in the presence of organics.

Adsorption, hydrogenation and dehydrogenation of C2H on a CoCu bimetallic layer

NASA Astrophysics Data System (ADS)

Wu, Donghai; Yuan, Jinyun; Yang, Baocheng; Chen, Houyang

2018-05-01

In this paper, adsorption, hydrogenation and dehydrogenation of C2H on a single atomic layer of bimetallic CoCu were investigated using first-principles calculations. The CoCu bimetallic layer is formed by Cu replacement of partial Co atoms on the top layer of a Co(111) surface. Our adsorption and reaction results showed those sites, which have stronger adsorption energy of C2H, possess higher reactivity. The bimetallic layer possesses higher reactivity than either of the pure monometallic layer. A mechanism of higher reactivity of the bimetallic layer is proposed and identified, i.e. in the bimetallic catalyst, the catalytic performance of one component is promoted by the second component, and in our work, the catalytic performance of Co atoms in the bimetallic layer are improved by introducing Cu atoms, lowing the activation barrier of the reaction of C2H. The bimetallic layer could tune adsorption and reaction of C2H by modulating the ratio of Co and Cu. Results of adsorption energies and adsorption configurations reveal that C2H prefers to be adsorbed in parallel on both the pure Co metallic and CoCu bimetallic layers, and Co atoms in subsurface which support the metallic or bimetallic layer have little effect on C2H adsorption. For hydrogenation reactions, the products greatly depend on the concentration and initial positions of hydrogen atoms, and the C2H hydrogenation forming acetylene is more favorable than forming vinylidene in both thermodynamics and kinetics. This study would provide fundamental guidance for hydrocarbon reactions on Co-based and/or Cu-based bimetallic surface chemistry and for development of new bimetallic catalysts.

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite.

PubMed

Al-Ghouti, M A; Khraisheh, M A M; Ahmad, M N; Allen, S J

2007-07-19

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity

PROBING REACTIVITY OF DISSOLVED ORGANIC MATTER FOR DISINFECTION BY-PRODUCT FORMATION USING XAD-8 RESIN ADSORPTION AND ULTRAFILTRATION FRACTIONATION. (R828045)

EPA Science Inventory

The disinfection by-product (DBP) reactivity (yield and speciation upon reaction with chlorine) of dissolved organic matter (DOM) isolated from two surface waters was investigated. The source waters, each having significantly different specific ultraviolet absorbance (SUVA

Adsorption of arsenic(III) into modified lamellar Na-magadiite in aqueous medium—Thermodynamic of adsorption process

NASA Astrophysics Data System (ADS)

Guerra, Denis Lima; Pinto, Alane Azevedo; Airoldi, Claudio; Viana, Rúbia Ribeiro

2008-12-01

Synthetic Na-magadiite sample was used for organofunctionalization process with N-propyldiethylenetrimethoxysilane and bis[3-(triethoxysilyl)propyl]tetrasulfide, after expanding the interlayer distance with polar organic solvents such as dimethylsulfoxide (DMSO). The resulted materials were submitted to process of adsorption with arsenic solution at pH 2.0 and 298±1 K. The adsorption isotherms were adjusted using a modified Langmuir equation with regression nonlinear; the net thermal effects obtained from calorimetric titration measurements were adjusted to a modified Langmuir equation. The adsorption process was exothermic (Δ intH=-4.15-5.98 kJ mol -1) accompanied by increase in entropy (Δ intS=41.32-62.20 J k -1 mol -1) and Gibbs energy (Δ intG=-22.44-24.56 kJ mol -1). The favorable values corroborate with the arsenic (III)/basic reactive centers interaction at the solid-liquid interface in the spontaneous process.

A molecular investigation of adsorption onto mineral pigments

NASA Astrophysics Data System (ADS)

Ninness, Brian J.

Pigment suspensions are important in several processes such as ceramics, paints, inks, and coatings. In the wet state, pigments are combined with a variety of chemical species such as polymers, surfactants, and polyelectrolytes which produce a complex colloidal system. The adsorption, desorption, and redistribution of these species at the pigment-aqueous solution interface can have an impact on the behavior in both the wet state or its final dried state. The goal of this work is to establish a molecular picture of the adsorption properties of these pigmented systems. A novel in situ infrared technique has been developed which allows the detection of adsorbed surface species on pigment particles in an aqueous environment. The technique involves the use of a polymeric binder to anchor the colloidal pigment particles to the surface of an internal reflection element (IRE). The binder only weakly perturbs about 25% of the reactive surface sites (hydroxyl groups) on silica. The reaction of succinic anhydride with an aminosilanized silica surface has been quantified using this technique. The adsorption dynamics of the cationic surfactant cetyltrimethylammonium bromide (C16TAB) at the TiO2-aqueous solution interface has been investigated using Fourier transform infrared-attenuated total reflection spectroscopy (FTIR-ATR) and electrokinetic analysis. At low bulk concentrations, C16TAB is shown to adsorb as isolated islands with a "defective" bilayer structure. Anionic probe molecules are shown to effectively "tune" the adsorbed surfactant microstructure. The results indicate that the structure of the adsorbed surfactant layer, and not the amount of adsorbed surfactant, dictates the subsequent adsorption behavior of the system. Atomic Layer Deposition is used to deposit a TiO2 layer onto the surfaces of silica and kaolin pigments. The process involves the cyclic reaction sequence of the vapors of TiCl4 and H2O. Three complete deposition cycles are needed before the surfaces

Adsorption of thiophene on silica-supported Mo clusters

NASA Astrophysics Data System (ADS)

Komarneni, M.; Kadossov, E.; Justin, J.; Lu, M.; Burghaus, U.

2010-07-01

The adsorption/decomposition kinetics/dynamics of thiophene has been studied on silica-supported Mo and MoS x clusters. Two-dimensional cluster formation at small Mo exposures and three-dimensional cluster growth at larger exposures would be consistent with the Auger electron spectroscopy (AES) data. Thermal desorption spectroscopy (TDS) indicates two reaction pathways. H 4C 4S desorbs molecularly at 190-400 K. Two TDS features were evident and could be assigned to molecularly on Mo sites, and S sites adsorbed thiophene. Assuming a standard preexponential factor (ν = 1 × 10 13/s) for first-order kinetics, the binding energies for adsorption on Mo (sulfur) sites amount to 90 (65) kJ/mol for 0.4 ML Mo exposure and 76 (63) kJ/mol for 2 ML Mo. Thus, smaller clusters are more reactive than larger clusters for molecular adsorption of H 4C 4S. The second reaction pathway, the decomposition of thiophene, starts at 250 K. Utilizing multimass TDS, H 2, H 2S, and mostly alkynes are detected in the gas phase as decomposition products. H 4C 4S bond activation results in partially sulfided Mo clusters as well as S and C residuals on the surface. S and C poison the catalyst. As a result, with an increasing number of H 4C 4S adsorption/desorption cycles, the uptake of molecular thiophene decreases as well as the H 2 and H 2S production ceases. Thus, silica-supported sulfided Mo clusters are less reactive than metallic clusters. The poisoned catalyst can be partially reactivated by annealing in O 2. However, Mo oxides also appear to form, which passivate the catalyst further. On the other hand, while annealing a used catalyst in H/H 2, it is poisoned even more (i.e., the S AES signal increases). By means of adsorption transients, the initial adsorption probability, S0, of C 4H 4S has been determined. At thermal impact energies ( Ei = 0.04 eV), S0 for molecular adsorption amounts to 0.43 ± 0.03 for a surface temperature of 200 K. S0 increases with Mo cluster size, obeying the

Surface Complexation Modeling of U(VI) Adsorption onto Savannah River Site Sediments

NASA Astrophysics Data System (ADS)

Dong, W.; Wan, J.; Tokunaga, T. K.; Denham, M.; Davis, J.; Hubbard, S. S.

2011-12-01

The Savannah River Site (SRS) was a U.S. Department of Energy facility for plutonium production during the Cold War. Waste plumes containing low-level radioactivity and acidic waste solutions were discharged to a series of unlined seepage basins in the F-Area of the SRS from 1955 to 1988. Although the site has undergone many years of active remediation, the groundwater remains acidic, and the concentrations of U and other radionuclides are still significantly higher than their Maximum Contaminant Levels (MCLs). The objective of this effort is to understand and predict U(VI) mobility in acidic waste plumes through developing surface complexation models (SCMs). Laboratory batch experiments were conducted to evaluate U adsorption behavior over the pH range of 3.0 to 9.5. Ten sorbent samples were selected including six contaminated sediment samples from three boreholes drilled within the plume and along the groundwater flow direction, two uncontaminated (pristine) sediment samples from a borehole outside of the plume, and two reference minerals, goethite and kaolinite (identified as the dominant minerals in the clay size fraction of the F-Area sediments). The results show that goethite and kaolinite largely control U partitioning behavior. In comparison with the pristine sediment, U(VI) adsorption onto contaminated sediments exhibits adsorption edges shifted toward lower pH by about 1.0 unit (e.g., from pH≈4.5 to pH≈3.5). We developed a SCMs based component additivity (CA) approach, which can successfully predict U(VI) adsorption onto uncontaminated SRS sediments. However, application of the same SCMs based CA approach to contaminated sediments resulted in underestimates of U(VI) adsorption at acidic pH conditions. The model sensitivity analyses indicate that both goethite and kaolinite surfaces co-contributed to U(VI) adsorption under acidic pH conditions. In particular, the exchange sites of clay minerals might play an important role in adsorption of U(VI) at p

Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

PubMed Central

Dutta, Sajal Kanti; Chakraborty, Saikat

2016-01-01

Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale–the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80–90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5–6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation. PMID:27905534

Pore-scale dynamics of enzyme adsorption, swelling and reactive dissolution determine sugar yield in hemicellulose hydrolysis for biofuel production

NASA Astrophysics Data System (ADS)

Dutta, Sajal Kanti; Chakraborty, Saikat

2016-12-01

Hemicelluloses are the earth’s second most abundant structural polymers, found in lignocellulosic biomass. Efficient enzymatic depolymerization of xylans by cleaving their β-(1 → 4)-glycosidic bonds to produce soluble sugars is instrumental to the cost-effective production of liquid biofuels. Here we show that the multi-scale two-phase process of enzymatic hydrolysis of amorphous hemicelluloses is dominated by its smallest scale-the pores. In the crucial first five hours, two to fourfold swelling of the xylan particles allow the enzymes to enter the pores and undergo rapid non-equilibrium adsorption on the pore surface before they hydrolyze the solid polymers, albeit non-competitively inhibited by the products xylose and xylobiose. Rapid pore-scale reactive dissolution increases the solid carbohydrate’s porosity to 80-90%. This tightly coupled experimental and theoretical study quantifies the complex temporal dynamics of the transport and reaction processes coupled across scales and phases to show that this unique pore-scale phenomenon can be exploited to accelerate the depolymerization of hemicelluloses to monomeric sugars in the first 5-6 h. We find that an ‘optimal substrate loading’ of 5 mg/ml (above which substrate inhibition sets in) accelerates non-equilibrium enzyme adsorption and solid hemicellulose depolymerization at the pore-scale, which contributes three-quarters of the soluble sugars produced for bio-alcohol fermentation.

Adsorption energies of benzene on close packed transition metal surfaces using the random phase approximation

NASA Astrophysics Data System (ADS)

Garrido Torres, José A.; Ramberger, Benjamin; Früchtl, Herbert A.; Schaub, Renald; Kresse, Georg

2017-11-01

The adsorption energy of benzene on various metal substrates is predicted using the random phase approximation (RPA) for the correlation energy. Agreement with available experimental data is systematically better than 10% for both coinage and reactive metals. The results are also compared with more approximate methods, including van der Waals density functional theory (DFT), as well as dispersion-corrected DFT functionals. Although dispersion-corrected DFT can yield accurate results, for instance, on coinage metals, the adsorption energies are clearly overestimated on more reactive transition metals. Furthermore, coverage dependent adsorption energies are well described by the RPA. This shows that for the description of aromatic molecules on metal surfaces further improvements in density functionals are necessary, or more involved many-body methods such as the RPA are required.

Recovery oriented phosphorus adsorption process in decentralized advanced Johkasou.

PubMed

Ebie, Y; Kondo, T; Kadoya, N; Mouri, M; Maruyama, O; Noritake, S; Inamori, Y; Xu, K

2008-01-01

Decentralized advanced wastewater treatment using adsorption and desorption process for recovery and recycling oriented phosphorus removal was developed. Adsorbent particles made of zirconium were set in a column, and it was installed as subsequent stage of BOD and nitrogen removal type Johkasou, a household domestic wastewater treatment facility. The water quality of the effluent of adsorption column in a number of experimental sites was monitored. The effluent phosphorus concentration was kept below 1 mg l(-1) during 90 days at all the sites. Furthermore, over 80% of the sites achieved 1 mg l(-1) of T-P during 200 days. This adsorbent was durable, and deterioration of the particles was not observed over a long duration. The adsorbent collected from each site was immersed in alkali solution to desorb phosphorus. Then the adsorbent was reactivated by soaking in acid solution. The reactivated adsorbent was reused and showed almost the same phosphorus adsorption capacity as a new one. Meanwhile, the desorbed phosphorus was recovered with high purity as trisodium phosphate by crystallization. It is proposed as a new decentralized system for recycling phosphorus that paves the way to high-purity recovery of finite phosphorus. IWA Publishing 2008.

Probing surface sites of TiO2: reactions with [HRe(CO)5] and [CH3Re(CO)5].

PubMed

Lobo-Lapidus, Rodrigo J; Gates, Bruce C

2010-10-04

Two carbonyl complexes of rhenium, [HRe(CO)(5)] and [CH(3)Re(CO)(5)], were used to probe surface sites of TiO(2) (anatase). These complexes were adsorbed from the gas phase onto anatase powder that had been treated in flowing O(2) or under vacuum to vary the density of surface OH sites. Infrared (IR) spectra demonstrate the variation in the number of sites, including Ti(+3)-OH and Ti(+4)-OH. IR and extended X-ray absorption fine structure (EXAFS) spectra show that chemisorption of the rhenium complexes led to their decarbonylation, with formation of surface-bound rhenium tricarbonyls, when [HRe(CO)(5)] was adsorbed, or rhenium tetracarbonyls, when [CH(3)Re(CO)(5)] was adsorbed. These reactions were accompanied by the formation of water and surface carbonates and removal of terminal hydroxyl groups associated with Ti(+3) and Ti(+4) ions on the anatase. Data characterizing the samples after adsorption of [HRe(CO)(5)] or [CH(3)Re(CO)(5)] determined a ranking of the reactivity of the surface OH sites, with the Ti(+3)-OH groups being the more reactive towards the rhenium complexes but the less likely to be dehydroxylated. The two rhenium pentacarbonyl probes provided complementary information, suggesting that the carbonate species originate from carbonyl ligands initially bonded to the rhenium and from hydroxyl groups of the titania surface, with the reaction leading to the formation of water and bridging hydroxyl groups on the titania. The results illustrate the value of using a family of organometallic complexes as probes of oxide surface sites.

The influence of CO adsorption on the surface composition of cobalt/palladium alloys

NASA Astrophysics Data System (ADS)

Murdoch, A.; Trant, A. G.; Gustafson, J.; Jones, T. E.; Noakes, T. C. Q.; Bailey, P.; Baddeley, C. J.

2016-04-01

Segregation induced by the adsorption of gas phase species can strongly influence the composition of bimetallic surfaces and can therefore play an important role in influencing heterogeneous catalytic reactions. The addition of palladium to cobalt catalysts has been shown to promote Fischer Tropsch catalysis. We investigate the adsorption of CO onto bimetallic CoPd surfaces on Pd{111} using a combination of reflection absorption infrared spectroscopy and medium energy ion scattering. The vibrational frequency of adsorbed CO provides crucial information on the adsorption sites adopted by CO and medium energy ion scattering probes the surface composition before and after CO exposure. We show that cobalt segregation is induced by CO adsorption and rationalise these observations in terms of the strength of adsorption of CO in various surface adsorption sites.

Dynamics, Stability, and Adsorption States of Water on Oxidized RuO 2 (110)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Manh-Thuong; Mu, Rentao; Cantu, David C.

Identifying and understanding how excess oxygen atoms affect the adsorption of water on metal oxides is crucial for their use in water splitting. Here, by means of high-resolution scanning tunneling microscopy and density-functional calculations, we show that excess oxygen atoms on the stoichiometric RuO2(110) significantly change the clustering, conformation, and deprotonation equilibrium of adsorbed water. We considered two reactive scenarios during which the stoichiometric surface was exposed to: (i) first to oxygen followed by water, and (ii) first to water followed by oxygen. In both cases the [OH-OH] complex on Ru rows is the dominant species, showing a significant differencemore » from water-only adsorption on the stoichiometric surface in which the [OH-H2O] species is found to be prevalent. Surface reactivity at almost full O coverage is also addressed; there we show that site selectivity of the surface for H adsorption and dissociation of H2O is hindered, notwithstanding the increase of the dynamical motion of both species. We found that the work function of RuO2 can serve as a descriptor for the reactivity of this surface to water and its constituents.« less

Imaging lysosomal highly reactive oxygen species and lighting up cancer cells and tumors enabled by a Si-rhodamine-based near-infrared fluorescent probe.

PubMed

Zhang, Hongxing; Liu, Jing; Liu, Chenlu; Yu, Pengcheng; Sun, Minjia; Yan, Xiaohan; Guo, Jian-Ping; Guo, Wei

2017-07-01

Lysosomes have recently been regarded as the attractive pharmacological targets for selectively killing of cancer cells via lysosomal cell death (LCD) pathway that is closely associated with reactive oxygen species (ROS). However, the details on the ROS-induced LCD of cancer cells are still poorly understood, partially due to the absence of a lysosome-targetable, robust, and biocompatible imaging tool for ROS. In this work, we brought forward a Si-rhodamine-based fluorescent probe, named PSiR, which could selectively and sensitively image the pathologically more relavent highly reactive oxygen species (hROS: HClO, HO, and ONOO - ) in lysosomes of cancer cells. Compared with many of the existing hROS fluorescent probes, its superiorities are mainly embodied in the high stability against autoxidation and photoxidation, near-infrared exitation and emission, fast fluorescence off-on response, and specific lysosomal localization. Its practicality has been demonstrated by the real-time imaging of hROS generation in lysosomes of human non-small-cell lung cancer cells stimulated by anticancer drug β-lapachone. Moreover, the probe was sensitive enough for basal hROS in cancer cells, allowing its further imaging applications to discriminate not only cancer cells from normal cells, but also tumors from healthy tissues. Overall, our results strongly indicated that PSiR is a very promising imaging tool for the studies of ROS-related LCD of cancer cells, screening of new anticancer drugs, and early diagnosis of cancers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Interaction of polyhydroxy fullerenes with ferrihydrite: adsorption and aggregation.

PubMed

Liu, Jing; Zhu, Runliang; Xu, Tianyuan; Laipan, Mingwang; Zhu, Yanping; Zhou, Qing; Zhu, Jianxi; He, Hongping

2018-02-01

The rapid development of nanoscience and nanotechnology, with thousands types of nanomaterials being produced, will lead to various environmental impacts. Thus, understanding the behaviors and fate of these nanomaterials is essential. This study focused on the interaction between polyhydroxy fullerenes (PHF) and ferrihydrite (Fh), a widespread iron (oxyhydr)oxide nanomineral and geosorbent. Our results showed that PHF were effectively adsorbed by Fh. The adsorption isotherm fitted the D-R model well, with an adsorption capacity of 67.1mg/g. The adsorption mean free energy of 10.72kJ/mol suggested that PHF were chemisorbed on Fh. An increase in the solution pH and a decrease of the Fh surface zeta potential were observed after the adsorption of PHF on Fh; moreover, increasing initial solution pH led to a reduction of adsorption. The Fourier transform infrared spectra detected a red shift of C-O stretching from 1075 to 1062cm -1 and a decrease of Fe-O bending, implying the interaction between PHF oxygenic functional groups and Fh surface hydroxyls. On the other hand, PHF affected the aggregation and reactivity of Fh by changing its surface physicochemical properties. Aggregation of PHF and Fh with individual particle sizes increasing from 2nm to larger than 5nm was measured by atomic force microscopy. The uniform distribution of C and Fe suggested that the aggregates of Fh were possibly bridged by PHF. Our results indicated that the interaction between PHF and Fh could evidently influence the migration of PHF, as well as the aggregation and reactivity of Fh. Copyright © 2017. Published by Elsevier B.V.

NH3 adsorption on anatase-TiO2(101)

NASA Astrophysics Data System (ADS)

Koust, Stig; Adamsen, Kræn C.; Kolsbjerg, Esben Leonhard; Li, Zheshen; Hammer, Bjørk; Wendt, Stefan; Lauritsen, Jeppe V.

2018-03-01

The adsorption of ammonia on anatase TiO2 is of fundamental importance for several catalytic applications of TiO2 and for probing acid-base interactions. Utilizing high-resolution scanning tunneling microscopy (STM), synchrotron X-ray photoelectron spectroscopy, temperature-programmed desorption (TPD), and density functional theory (DFT), we identify the adsorption mode and quantify the adsorption strength on the anatase TiO2(101) surface. It was found that ammonia adsorbs non-dissociatively as NH3 on regular five-fold coordinated titanium surface sites (5f-Ti) with an estimated exothermic adsorption energy of 1.2 eV for an isolated ammonia molecule. For higher adsorbate coverages, the adsorption energy progressively shifts to smaller values, due to repulsive intermolecular interactions. The repulsive adsorbate-adsorbate interactions are quantified using DFT and autocorrelation analysis of STM images, which both showed a repulsive energy of ˜50 meV for nearest neighbor sites and a lowering in binding energy for an ammonia molecule in a full monolayer of 0.28 eV, which is in agreement with TPD spectra.

Protein recognition by a pattern-generating fluorescent molecular probe.

PubMed

Pode, Zohar; Peri-Naor, Ronny; Georgeson, Joseph M; Ilani, Tal; Kiss, Vladimir; Unger, Tamar; Markus, Barak; Barr, Haim M; Motiei, Leila; Margulies, David

2017-12-01

Fluorescent molecular probes have become valuable tools in protein research; however, the current methods for using these probes are less suitable for analysing specific populations of proteins in their native environment. In this study, we address this gap by developing a unimolecular fluorescent probe that combines the properties of small-molecule-based probes and cross-reactive sensor arrays (the so-called chemical 'noses/tongues'). On the one hand, the probe can detect different proteins by generating unique identification (ID) patterns, akin to cross-reactive arrays. On the other hand, its unimolecular scaffold and selective binding enable this ID-generating probe to identify combinations of specific protein families within complex mixtures and to discriminate among isoforms in living cells, where macroscopic arrays cannot access. The ability to recycle the molecular device and use it to track several binding interactions simultaneously further demonstrates how this approach could expand the fluorescent toolbox currently used to detect and image proteins.

Protein recognition by a pattern-generating fluorescent molecular probe

NASA Astrophysics Data System (ADS)

Pode, Zohar; Peri-Naor, Ronny; Georgeson, Joseph M.; Ilani, Tal; Kiss, Vladimir; Unger, Tamar; Markus, Barak; Barr, Haim M.; Motiei, Leila; Margulies, David

2017-12-01

Fluorescent molecular probes have become valuable tools in protein research; however, the current methods for using these probes are less suitable for analysing specific populations of proteins in their native environment. In this study, we address this gap by developing a unimolecular fluorescent probe that combines the properties of small-molecule-based probes and cross-reactive sensor arrays (the so-called chemical 'noses/tongues'). On the one hand, the probe can detect different proteins by generating unique identification (ID) patterns, akin to cross-reactive arrays. On the other hand, its unimolecular scaffold and selective binding enable this ID-generating probe to identify combinations of specific protein families within complex mixtures and to discriminate among isoforms in living cells, where macroscopic arrays cannot access. The ability to recycle the molecular device and use it to track several binding interactions simultaneously further demonstrates how this approach could expand the fluorescent toolbox currently used to detect and image proteins.

Chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot after reactive gas probing using diffuse reflectance FTIR spectroscopy (DRIFTS).

PubMed

Tapia, A; Salgado, M S; Martín, M P; Rodríguez-Fernández, J; Rossi, M J; Cabañas, B

2017-03-01

A chemical characterization of diesel and hydrotreated vegetable oil (HVO) soot has been developed using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) before and after the reaction with different probe gases. Samples were generated under combustion conditions corresponding to an urban operation mode of a diesel engine and were reacted with probe gas-phase molecules in a Knudsen flow reactor. Specifically, NH 2 OH, O 3 and NO 2 were used as reactants (probes) and selected according to their reactivities towards specific functional groups on the sample surface. Samples of previously ground soot were diluted with KBr and were introduced in a DRIFTS accessory. A comparison between unreacted and reacted soot samples was made in order to establish chemical changes on the soot surface upon reaction. It was concluded that the interface of diesel and HVO soot before reaction mainly consists polycyclic aromatic hydrocarbons, nitro and carbonyl compounds, as well as ether functionalities. The main difference between both soot samples was observed in the band of the C=O groups that in diesel soot was observed at 1719 cm -1 but not in HVO soot. After reaction with probe gases, it was found that nitro compounds remain on the soot surface, that the degree of unsaturation decreases for reacted samples, and that new spectral bands such as hydroxyl groups are observed.

Arsenate adsorption mechanisms at the allophane - Water interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2005-01-01

We investigated arsenate (As(V)) reactivity and surface speciation on amorphous aluminosilicate mineral (synthetic allophane) surfaces using batch adsorption experiments, powder X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The adsorption isotherm experiments indicated that As(V) uptake increased with increasing [As(V)]0 from 50 to 1000 ??M (i.e., Langmuir type adsorption isotherm) and that the total As adsorption slightly decreased with increasing NaCl concentrations from 0.01 to 0.1 M. Arsenate adsorption was initially (0-10 h) rapid followed by a slow continuum uptake, and the adsorption processes reached the steady state after 720 h. X-ray absorption spectroscopic analyses suggest that As(V) predominantly forms bidentate binuclear surface species on aluminum octahedral structures, and these species are stable up to 11 months. Solubility calculations and powder XRD analyses indicate no evidence of crystalline AI-As(V) precipitates in the experimental systems. Overall, macroscopic and spectroscopic evidence suggest that the As(V) adsorption mechanisms at the allophane-water interface are attributable to ligand exchange reactions between As(V) and surface-coordinated water molecules and hydroxyl and silicate ions. The research findings imply that dissolved tetrahedral oxyanions (e.g., H2PO42- and H2AsO42-) are readily retained on amorphous aluminosilicate minerals in aquifer and soils at near neutral pH. The innersphere adsorption mechanisms might be important in controlling dissolved arsenate and phosphate in amorphous aluminosilicate-rich low-temperature geochemical environments. ?? 2005 American Chemical Society.

Parameters estimation for reactive transport: A way to test the validity of a reactive model

NASA Astrophysics Data System (ADS)

Aggarwal, Mohit; Cheikh Anta Ndiaye, Mame; Carrayrou, Jérôme

The chemical parameters used in reactive transport models are not known accurately due to the complexity and the heterogeneous conditions of a real domain. We will present an efficient algorithm in order to estimate the chemical parameters using Monte-Carlo method. Monte-Carlo methods are very robust for the optimisation of the highly non-linear mathematical model describing reactive transport. Reactive transport of tributyltin (TBT) through natural quartz sand at seven different pHs is taken as the test case. Our algorithm will be used to estimate the chemical parameters of the sorption of TBT onto the natural quartz sand. By testing and comparing three models of surface complexation, we show that the proposed adsorption model cannot explain the experimental data.

Cysteine and cystine adsorption on FeS2(100)

NASA Astrophysics Data System (ADS)

Suzuki, Teppei; Yano, Taka-aki; Hara, Masahiko; Ebisuzaki, Toshikazu

2018-08-01

Iron pyrite (FeS2) is the most abundant metal sulfide on Earth. Owing to its reactivity and catalytic activity, pyrite has been studied in various research fields such as surface science, geochemistry, and prebiotic chemistry. Importantly, native iron-sulfur clusters are typically coordinated by cysteinyl ligands of iron-sulfur proteins. In the present paper, we study the adsorption of L-cysteine and its oxidized dimer, L-cystine, on the FeS2 surface, using electronic structure calculations based density functional theory and Raman spectroscopy measurements. Our calculations suggest that sulfur-deficient surfaces play an important role in the adsorption of cysteine and cystine. In the thiol headgroup adsorption on the sulfur-vacancy site, dissociative adsorption is found to be energetically favorable compared with molecular adsorption. In addition, the calculations indicate that, in the cystine adsorption on the defective surface under vacuum conditions, the formation of the S-Fe bond is energetically favorable compared with molecular adsorption. Raman spectroscopic measurements suggest the formation of cystine molecules through the S-S bond on the pyrite surface in aqueous solution. Our results might have implications for chemical evolution at mineral surfaces on the early Earth and the origin of iron-sulfur proteins, which are believed to be one of the most ancient families of proteins.

Adsorption of pentacene on (100) vicinal surfaces: role of coordination, surface chemistry and vdWs effects

NASA Astrophysics Data System (ADS)

Matos, Jeronimo; Kara, Abdelkader

2015-03-01

In contrast to low miller index surfaces, vicinal surfaces are characterized by steps and step edges that not only present an interesting atomic landscape for the adsorption organic molecules, but also a unique electronic structure resulting in part from the low coordinated atoms at the step edges. The adsorption of pentacene on the stepped (511), (711), (911) surfaces (respectively 3, 4 and 5-atom wide terraces) of Cu and Ag (coinage transition metals); Pt (reactive transition metal); and Ni (reactive, magnetic transition metal) are studied using density functional theory, in order to investigate the support effects arising from differing surface chemistry. We compare the adsorption energy, adsorption geometry and electronic structure predicted by the PBE functional with those obtained from one of the optimized vdW-DF methods: optB88-vdW. Work supported by the U.S. Department of Energy Basic Energy Science under Contract No. DE-FG02-11ER16243.

Reactive multi-particle collision dynamics with reactive boundary conditions

NASA Astrophysics Data System (ADS)

Sayyidmousavi, Alireza; Rohlf, Katrin

2018-07-01

In the present study, an off-lattice particle-based method called the reactive multi-particle collision (RMPC) dynamics is extended to model reaction-diffusion systems with reactive boundary conditions in which the a priori diffusion coefficient of the particles needs to be maintained throughout the simulation. To this end, the authors have made use of the so-called bath particles whose purpose is only to ensure proper diffusion of the main particles in the system. In order to model partial adsorption by a reactive boundary in the RMPC, the probability of a particle being adsorbed, once it hits the boundary, is calculated by drawing an analogy between the RMPC and Brownian Dynamics. The main advantages of the RMPC compared to other molecular based methods are less computational cost as well as conservation of mass, energy and momentum in the collision and free streaming steps. The proposed approach is tested on three reaction-diffusion systems and very good agreement with the solutions to their corresponding partial differential equations is observed.

Characterization of tannery sludge activated carbon and its utilization in the removal of azo reactive dye.

PubMed

Geethakarthi, A; Phanikumar, B R

2012-03-01

The removal of azo Reactive Red 31(RR31) from synthetic dye solution using tannery sludge-developed activated carbon (TSC) was investigated. TSC was prepared from a combination of physical and chemical activation. The developed TSC was characterized by FT-IR, SEM, TG-DTA, specific surface area and zero point charge of pH (pH(zpc)). The isotherm models, kinetic models and thermodynamic parameters were also analysed to describe the adsorptive behaviour of TSC. The effect of contact time, initial dye concentration, carbon dosage, agitation speed, initial pH and temperature were carried out for batch adsorption studies. The isotherm plot of the dye RR31 on TSC fitted better with the Langmuir adsorption isotherm than the Freundlich model. The maximum monolayer adsorption capacity of TSC in the removal of RR31 ranged from 23.15 to 39.37 mg/g. The thermodynamic parameters showed the endothermic and physical nature of the Reactive Red 31 adsorption on TSC. The entropy and enthalpy values were 181.515 J/Kmol and 5.285 kJ/mol, respectively. The developed cationic tannery sludge carbon was found to be an effective adsorbent in the removal of the anionic azo reactive dye RR31.

Impact of inter-genotypic recombination and probe cross-reactivity on the performance of the Abbott RealTime HCV Genotype II assay for hepatitis C genotyping.

PubMed

Sridhar, Siddharth; Yip, Cyril C Y; Chan, Jasper F W; To, Kelvin K W; Cheng, Vincent C C; Yuen, Kwok-Yung

2018-05-01

The Abbott RealTime HCV Genotype II assay (Abbott-RT-HCV assay) is a real-time PCR based genotyping method for hepatitis C virus (HCV). This study measured the impact of inter-genotypic recombination and probe cross-reactivity on the performance of the Abbott-RT-HCV assay. 517 samples were genotyped using the Abbott-RT-HCV assay over a one-year period, 34 (6.6%) were identified as HCV genotype 1 without further subtype designation raising the possibility of inaccurate genotyping. These samples were subjected to confirmatory sequencing. 27 of these 34 (79%) samples were genotype 1b while five (15%) were genotype 6. One HCV isolate was an inter-genotypic 1a/4o recombinant. This is a novel natural HCV recombinant that has never been reported. Inter-genotypic recombination and probe cross-reactivity can affect the accuracy of the Abbott-RT-HCV assay, both of which have significant implications on antiviral regimen choice. Confirmatory sequencing of ambiguous results is crucial for accurate genotyping. Copyright © 2018 Elsevier Inc. All rights reserved.

Adsorption of Bromine on Gold Nanoclusters

NASA Astrophysics Data System (ADS)

Salvo, Christopher; Keagy, Josiah; Yarmoff, Jory

Small metal nanoclusters are extremely effective as catalysts, with rates that rival those of enzymes in biological systems. The first step in a catalytic reaction is the adsorption of a precursor molecule. The neutralization of alkali projectiles during low energy ion scattering (LEIS), which is acutely sensitive to the local electrostatic potential a few Å's above the surface, is used here to probe Au nanoclusters grown on SiO2 as they are reacted with Br2. Previous work had demonstrated very efficient neutralization in scattering from small catalytically active Au clusters, which was interpreted as an indication that the bare clusters are negatively charged. X-ray photoelectron spectroscopy and LEIS show little or no Br signal after exposing SiO2 and Au foil to Br2, suggesting that adsorption does not occur because the Br-Br bond does not break. Dissociative adsorption occurs rapidly, however, when small Au nanoclusters are reacted with Br2. 1.5 keV Na+ ions scattered from the Au clusters show a decrease in the neutralization probability as Br is reacted, indicating that adsorption results in charge being transferred from the cluster to the Br adatom. This material is based upon work supported by the National Science Foundation under CHE - 1611563.

Thermodynamic Analysis of Nickel(II) and Zinc(II) Adsorption to Biochar.

PubMed

Alam, Md Samrat; Gorman-Lewis, Drew; Chen, Ning; Flynn, Shannon L; Ok, Yong Sik; Konhauser, Kurt O; Alessi, Daniel S

2018-05-21

While numerous studies have investigated metal uptake from solution by biochar, few of these have developed a mechanistic understanding of the adsorption reactions that occur at the biochar surface. In this study, we explore a combined modeling and spectroscopic approach for the first time to describe the molecular level adsorption of Ni(II) and Zn(II) to five types of biochar. Following thorough characterization, potentiometric titrations were carried out to measure the proton (H + ) reactivity of each biochar, and the data was used to develop protonation models. Surface complexation modeling (SCM) supported by synchrotron-based extended X-ray absorption fine structure (EXAFS) was then used to gain insights into the molecular scale metal-biochar surface reactions. The SCM approach was combined with isothermal titration calorimetry (ITC) data to determine the thermodynamic driving forces of metal adsorption. Our results show that the reactivity of biochar toward Ni(II) and Zn(II) directly relates to the site densities of biochar. EXAFS along with FT-IR analyses, suggest that Ni(II) and Zn(II) adsorption occurred primarily through proton-active carboxyl (-COOH) and hydroxyl (-OH) functional groups on the biochar surface. SCM-ITC analyses revealed that the enthalpies of protonation are exothermic and Ni(II) and Zn(II) complexes with biochar surface are slightly exothermic to slightly endothermic. The results obtained from these combined approaches contribute to the better understanding of molecular scale metal adsorption onto the biochar surface, and will facilitate the further development of thermodynamics-based, predictive approaches to biochar removal of metals from contaminated water.

Removal of carbonyl sulfide using activated carbon adsorption.

PubMed

Sattler, Melanie L; Rosenberk, Ranjith Samuel

2006-02-01

Wastewater treatment plant odors are caused by compounds such as hydrogen sulfide (H2S), methyl mercaptans, and carbonyl sulfide (COS). One of the most efficient odor control processes is activated carbon adsorption; however, very few studies have been conducted on COS adsorption. COS is not only an odor causing compound but is also listed in the Clean Air Act as a hazardous air pollutant. Objectives of this study were to determine the following: (1) the adsorption capacity of 3 different carbons for COS removal; (2) the impact of relative humidity (RH) on COS adsorption; (3) the extent of competitive adsorption of COS in the presence of H2S; and (4) whether ammonia injection would increase COS adsorption capacity. Vapor phase react (VPR; reactivated), BPL (bituminous coal-based), and Centaur (physically modified to enhance H2S adsorption) carbons manufactured by Calgon Carbon Corp. were tested in three laboratory-scale columns, 6 in. in depth and 1 in. in diameter. Inlet COS concentrations varied from 35 to 49 ppmv (86-120 mg/m3). RHs of 17%, 30%, 50%, and 90% were tested. For competitive adsorption studies, H2S was tested at 60 ppmv, with COS at 30 ppmv. COS, RH, H2S, and ammonia concentrations were measured using an International Sensor Technology Model IQ-350 solid state sensor, Cole-Parmer humidity stick, Interscan Corp. 1000 series portable analyzer, and Drager Accuro ammonia sensor, respectively. It was found that the adsorption capacity of Centaur carbon for COS was higher than the other two carbons, regardless of RH. As humidity increased, the percentage of decrease in adsorption capacity of Centaur carbon, however, was greater than the other two carbons. The carbon adsorption capacity for COS decreased in proportion to the percentage of H2S in the gas stream. More adsorption sites appear to be available to H2S, a smaller molecule. Ammonia, which has been found to increase H2S adsorption capacity, did not increase the capacity for COS.

Interfacial adsorption in two-dimensional pure and random-bond Potts models.

PubMed

Fytas, Nikolaos G; Theodorakis, Panagiotis E; Malakis, Anastasios

2017-03-01

We use Monte Carlo simulations to study the finite-size scaling behavior of the interfacial adsorption of the two-dimensional square-lattice q-states Potts model. We consider the pure and random-bond versions of the Potts model for q=3,4,5,8, and 10, thus probing the interfacial properties at the originally continuous, weak, and strong first-order phase transitions. For the pure systems our results support the early scaling predictions for the size dependence of the interfacial adsorption at both first- and second-order phase transitions. For the disordered systems, the interfacial adsorption at the (disordered induced) continuous transitions is discussed, applying standard scaling arguments and invoking findings for bulk critical properties. The self-averaging properties of the interfacial adsorption are also analyzed by studying the infinite limit-size extrapolation of properly defined signal-to-noise ratios.

Time scale of random sequential adsorption.

PubMed

Erban, Radek; Chapman, S Jonathan

2007-04-01

A simple multiscale approach to the diffusion-driven adsorption from a solution to a solid surface is presented. The model combines two important features of the adsorption process: (i) The kinetics of the chemical reaction between adsorbing molecules and the surface and (ii) geometrical constraints on the surface made by molecules which are already adsorbed. The process (i) is modeled in a diffusion-driven context, i.e., the conditional probability of adsorbing a molecule provided that the molecule hits the surface is related to the macroscopic surface reaction rate. The geometrical constraint (ii) is modeled using random sequential adsorption (RSA), which is the sequential addition of molecules at random positions on a surface; one attempt to attach a molecule is made per one RSA simulation time step. By coupling RSA with the diffusion of molecules in the solution above the surface the RSA simulation time step is related to the real physical time. The method is illustrated on a model of chemisorption of reactive polymers to a virus surface.

Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets.

PubMed

Wang, Jun; Chen, Zaiming; Chen, Baoliang

2014-05-06

The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (Kd) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π-π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π-π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process.

Gas sampling system for reactive gas-solid mixtures

DOEpatents

Daum, Edward D.; Downs, William; Jankura, Bryan J.; McCoury, Jr., John M.

1989-01-01

An apparatus and method for sampling a gas containing a reactive particulate solid phase flowing through a duct and for communicating a representative sample to a gas analyzer. A sample probe sheath 32 with an angular opening 34 extends vertically into a sample gas duct 30. The angular opening 34 is opposite the gas flow. A gas sampling probe 36 concentrically located within sheath 32 along with calibration probe 40 partly extend in the sheath 32. Calibration probe 40 extends further in the sheath 32 than gas sampling probe 36 for purging the probe sheath area with a calibration gas during calibration.

Gas sampling system for reactive gas-solid mixtures

DOEpatents

Daum, Edward D.; Downs, William; Jankura, Bryan J.; McCoury, Jr., John M.

1990-01-01

An apparatus and method for sampling gas containing a reactive particulate solid phase flowing through a duct and for communicating a representative sample to a gas analyzer. A sample probe sheath 32 with an angular opening 34 extends vertically into a sample gas duct 30. The angular opening 34 is opposite the gas flow. A gas sampling probe 36 concentrically located within sheath 32 along with calibration probe 40 partly extends in the sheath 32. Calibration probe 40 extends further in the sheath 32 than gas sampling probe 36 for purging the probe sheath area with a calibration gas during calibration.

Nonlinear optical probe of biopolymer adsorption on colloidal particle surface: poly-L-lysine on polystyrene sulfate microspheres.

PubMed

Eckenrode, Heather M; Dai, Hai-Lung

2004-10-12

A nonlinear optical technique--second harmonic generation (SHG)--has been applied to characterize the adsorption of poly-L-lysine on micrometer size polystyrene particles, whose surface is covered with negatively charged sulfonate groups, in aqueous solutions. Adsorption behavior of the biopolymer with two chain lengths (14 and 75 amino acid units; PL14 and PL75) has been examined. Centrifugation experiments were also performed to support the adsorption measurements made using SHG. The adsorption free energies of the two polymers PL75 and PL14 are determined as -16.57 and -14.40 kcal/mol, respectively. The small difference in the adsorption free energies of the two chain lengths, however, leads to dramatic difference in the concentration needed for saturated surface coverage: nearly 50 times higher concentration is needed for the smaller polymer. Under acidic colloidal conditions, polylysine is found to adsorb in a relatively flat conformation on the surface. The surface area that each polylysine molecule occupies is nearly 1 order of magnitude larger than the size of the molecule in its extended form. The low adsorption density is likely a result from Coulombic repulsion between the positive charges on the amino acid units of PL. The measurements demonstrate the utility of SHG as an efficient and sensitive experimental approach for measuring adsorption characteristics of bio/macromolecules on colloidal particles and define surface and colloidal conditions for achieving maximum surface coverage of a widely used biopolymer. Copyright 2004 American Chemical Society

Tailoring oxide properties: An impact on adsorption characteristics of molecules and metals

NASA Astrophysics Data System (ADS)

Honkala, Karoliina

2014-12-01

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster's theoretically predicted ability to activate and dissociate O2 at the Au-MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O2, CO, NO2, and H2O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O2 dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H2O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide

Probing the molecular-level control of aluminosilicate dissolution: A sensitive solid-state NMR proxy for reactive surface area

NASA Astrophysics Data System (ADS)

Washton, Nancy M.; Brantley, Susan L.; Mueller, Karl T.

2008-12-01

For two suites of volcanic aluminosilicate glasses, the accessible and reactive sites for covalent attachment of the fluorine-containing (3,3,3-trifluoropropyl)dimethylchlorosilane (TFS) probe molecule were measured by quantitative 19F nuclear magnetic resonance (NMR) spectroscopy. The first set of samples consists of six rhyolitic and dacitic glasses originating from volcanic activity in Iceland and one rhyolitic glass from the Bishop Tuff, CA. Due to differences in the reactive species present on the surfaces of these glasses, variations in the rate of acid-mediated dissolution (pH 4) for samples in this suite cannot be explained by variations in geometric or BET-measured surface area. In contrast, the rates scale directly with the surface density of TFS-reactive sites as measured by solid-state NMR. These data are consistent with the inference that the TFS-reactive M-OH species on the glass surface, which are known to be non-hydrogen-bonded Q 3 groups, represent loci accessible to and affected by proton-mediated dissolution. The second suite of samples, originating from a chronosequence in Kozushima, Japan, is comprised of four rhyolites that have been weathered for 1.1, 1.8, 26, and 52 ka. The number of TFS-reactive sites per gram increases with duration of weathering in the laboratory for the "Icelandic" samples and with duration of field weathering for both "Icelandic" and Japanese samples. One hypothesis is consistent with these and published modeling, laboratory, and field observations: over short timescales, dissolution is controlled by fast-dissolving sites, but over long timescales, dissolution is controlled by slower-dissolving sites, the surface density of which is proportional to the number of TFS-reactive Q 3 sites. These latter sites are not part of a hydrogen-bonded network on the surface of the glasses, and measurement of their surface site density allows predictions of trends in reactive surface area. The TFS treatment method, which is easily

Probing adsorption of polyacrylamide-based polymers on anisotropic Basal planes of kaolinite using quartz crystal microbalance.

PubMed

Alagha, Lana; Wang, Shengqun; Yan, Lujie; Xu, Zhenghe; Masliyah, Jacob

2013-03-26

Quartz crystal microbalance with dissipation (QCM-D) was applied to investigate the adsorption characteristics of polyacrylamide-based polymers (PAMs) on anisotropic basal planes of kaolinite. Kaolinite basal planes were differentiated by depositing kaolinite nanoparticles (KNPs) on silica and alumina sensors in solutions of controlled pH values. Adsorption of an in-house synthesized organic-inorganic Al(OH)3-PAM (Al-PAM) as an example of cationic hybrid PAM and a commercially available partially hydrolyzed polyacrylamide (MF1011) as an example of anionic PAM was studied. Cationic Al-PAM was found to adsorb irreversibly and preferentially on tetrahedral silica basal planes of kaolinite. In contrast, anionic MF1011 adsorbed strongly on aluminum-hydroxy basal planes, while its adsorption on tetrahedral silica basal planes was weak and reversible. Adsorption study revealed that both electrostatic attraction and hydrogen-bonding mechanisms contribute to adsorption of PAMs on kaolinite. The adsorbed Al-PAM layer was able to release trapped water overtime and became more compact, while MF1011 film became more dissipative as backbones stretched out from kaolinite surface with minimal overlapping. Experimental results obtained from this study provide clear insights into the phenomenon that governs flocculation-based solid-liquid separation processes using multicomponent flocculants of anionic and cationic nature.

Adsorptive fractionation of dissolved organic matter (DOM) by carbon nanotubes.

PubMed

Engel, Maya; Chefetz, Benny

2015-02-01

Dissolved organic matter (DOM) and carbon nanotubes are introduced into aquatic environments. Thus, it is important to elucidate whether their interaction affects DOM amount and composition. In this study, the composition of DOM, before and after interactions with single-walled carbon nanotubes (SWCNTs), was measured and the adsorption affinity of the individual structural fractions of DOM to SWCNTs was investigated. Adsorption of DOM to SWCNTs was dominated by the hydrophobic acid fraction, resulting in relative enhancement of the hydrophilic character of non-adsorbed DOM. The preferential adsorption of the HoA fraction was concentration-dependent, increasing with increasing concentration. Adsorption affinities of bulk DOM calculated as the normalized sum of affinities of the individual structural fractions were similar to the measured affinities, suggesting that the structural fractions of DOM act as independent adsorbates. The altered DOM composition may affect the nature and reactivity of DOM in aquatic environments polluted with carbon nanotubes. Copyright © 2014 Elsevier Ltd. All rights reserved.

Solid-phase microextraction/gas chromatography-mass spectrometry method optimization for characterization of surface adsorption forces of nanoparticles.

PubMed

Omanovic-Miklicanin, Enisa; Valzacchi, Sandro; Simoneau, Catherine; Gilliland, Douglas; Rossi, Francois

2014-10-01

A complete characterization of the different physico-chemical properties of nanoparticles (NPs) is necessary for the evaluation of their impact on health and environment. Among these properties, the surface characterization of the nanomaterial is the least developed and in many cases limited to the measurement of surface composition and zetapotential. The biological surface adsorption index approach (BSAI) for characterization of surface adsorption properties of NPs has recently been introduced (Xia et al. Nat Nanotechnol 5:671-675, 2010; Xia et al. ACS Nano 5(11):9074-9081, 2011). The BSAI approach offers in principle the possibility to characterize the different interaction forces exerted between a NP's surface and an organic--and by extension biological--entity. The present work further develops the BSAI approach and optimizes a solid-phase microextraction gas chromatography-mass spectrometry (SPME/GC-MS) method which, as an outcome, gives a better-defined quantification of the adsorption properties on NPs. We investigated the various aspects of the SPME/GC-MS method, including kinetics of adsorption of probe compounds on SPME fiber, kinetic of adsorption of probe compounds on NP's surface, and optimization of NP's concentration. The optimized conditions were then tested on 33 probe compounds and on Au NPs (15 nm) and SiO2 NPs (50 nm). The procedure allowed the identification of three compounds adsorbed by silica NPs and nine compounds by Au NPs, with equilibrium times which varied between 30 min and 12 h. Adsorption coefficients of 4.66 ± 0.23 and 4.44 ± 0.26 were calculated for 1-methylnaphtalene and biphenyl, compared to literature values of 4.89 and 5.18, respectively. The results demonstrated that the detailed optimization of the SPME/GC-MS method under various conditions is a critical factor and a prerequisite to the application of the BSAI approach as a tool to characterize surface adsorption properties of NPs and therefore to draw any further

Water adsorption isotherms on porous onionlike carbonaceous particles. Simulations with the grand canonical Monte Carlo method

NASA Astrophysics Data System (ADS)

Hantal, György; Picaud, Sylvain; Hoang, Paul N. M.; Voloshin, Vladimir P.; Medvedev, Nikolai N.; Jedlovszky, Pál

2010-10-01

The grand canonical Monte Carlo method is used to simulate the adsorption isotherms of water molecules on different types of model soot particles. These soot models are constructed by first removing atoms from onion-fullerene structures in order to create randomly distributed pores inside the soot, and then performing molecular dynamics simulations, based on the reactive adaptive intermolecular reactive empirical bond order (AIREBO) description of the interaction between carbon atoms, to optimize the resulting structures. The obtained results clearly show that the main driving force of water adsorption on soot is the possibility of the formation of new water-water hydrogen bonds with the already adsorbed water molecules. The shape of the calculated water adsorption isotherms at 298 K strongly depends on the possible confinement of the water molecules in pores of the carbonaceous structure. We found that there are two important factors influencing the adsorption ability of soot. The first of these factors, dominating at low pressures, is the ability of the soot of accommodating the first adsorbed water molecules at strongly hydrophilic sites. The second factor concerns the size and shape of the pores, which should be such that the hydrogen bonding network of the water molecules filling them should be optimal. This second factor determines the adsorption properties at higher pressures.

Protein Adsorption to Titanium and Zirconia Using a Quartz Crystal Microbalance Method

PubMed Central

Kusakawa, You

2017-01-01

Protein adsorption onto titanium (Ti) or zirconia (ZrO2) was evaluated using a 27 MHz quartz crystal microbalance (QCM). As proteins, fibronectin (Fn), a cell adhesive protein, and albumin (Alb), a cell adhesion-inhibiting protein, were evaluated. The Ti and ZrO2 sensors for QCM were characterized by atomic force microscopy and electron probe microanalysis observation, measurement of contact angle against water, and surface roughness. The amounts of Fn and Alb adsorbed onto the Ti and ZrO2 sensors and apparent reaction rate were obtained using QCM measurements. Ti sensor showed greater adsorption of Fn and Alb than the ZrO2 sensor. In addition, amount of Fn adsorbed onto the Ti or ZrO2 sensors was higher than that of Alb. The surface roughness and hydrophilicity of Ti or ZrO2 may influence the adsorption of Fn or Alb. With regard to the adsorption rate, Alb adsorbed more rapidly than Fn onto Ti. Comparing Ti and ZrO2, Alb adsorption rate to Ti was faster than that to ZrO2. Fn adsorption will be effective for cell activities, but Alb adsorption will not. QCM method could simulate in vivo Fn and Alb adsorption to Ti or ZrO2. PMID:28246591

Adsorption of water, sulfates and chloride on arsenopyrite surface

NASA Astrophysics Data System (ADS)

Silva, Juliana C. M.; dos Santos, Egon C.; de Oliveira, Aline; Heine, Thomas; De Abreu, Heitor A.; Duarte, Hélio A.

2018-03-01

Arsenopyrite is one of the sulfide minerals responsible for acid rock drainage (ARD) and is one of the most hazardous in regions affected by mining activities. This phenomenon involves complex reaction mechanism. Although it is intensely investigated, there is a lack of consensus concerning the reaction mechanisms and more information is still necessary. In this work, the adsorption of water, hydrochloric acid, and sulfuric acid on arsenopyrite (001) surface was investigated by means of Density Functional calculations and the results compared to other sulfides aiming to understand the mineral/water interface. The interaction of the chemical species with the (001) FeAsS surface is the first step to understand the intricate oxidation mechanism of arsenopyrite. Molecular water adsorption on (001) FeAsS is more favored than the adsorption of sulfate favoring the dissolution of sulfates and enhancing its oxidation. The estimated adsorption energies of water, sulfates and chloride on other sulfide minerals are compared with the estimated values for arsenopyrite and the chemical reactivity differences discussed in detail.

The mirage effect to probe the adsorption of organic molecules on the surface of the mass standards

NASA Astrophysics Data System (ADS)

Taillade, F.; Silva, M. Z.; Lepoutre, F.; Lecollinet, M.; Pinot, P.

2000-05-01

Among all the basic SI units, the mass unit is the only one to be defined in terms of a material standard: a prototype called K. All the industrial countries possess their own standards which were compared to the K during the last international comparison showing that unknown evolution occurs, but the adsorption-desorption of cleaning products plays a relatively important role. A few years ago, several laboratories in the U.S.A., Germany, and France reported interesting results of photothermal measurements to detect desorption at normal temperature and pressure (NTP). This paper presents a mirage set-up built to detect the film of condensable gasses on metallic surfaces at NTP conditions. In order to quantify these measurements, an inverse method has been developed to determine the adsorption isotherm involved in the physical process of adsorption-desorption and the linked parameters such as absorbability, type of adsorption, and differential heat of adsorption. The results will be discussed to imagine possible tracks to reduce the instabilities of the standards in the future and for possible new definitions of standards built with silicon.

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE PAGES

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.; ...

2018-01-19

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Trends in adsorption of electrocatalytic water splitting intermediates on cubic ABO 3 oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Montoya, Joseph H.; Doyle, Andrew D.; Nørskov, Jens K.

The reactivity of solid oxide surfaces towards adsorption of oxygen and hydrogen is a key metric for the design of new catalysts for electrochemical water splitting. Here, in this paper, we report on trends in the adsorption energy of different adsorbed intermediates derived from the oxidation and reduction of water for ternary ABO 3 oxides in the cubic perovskite structure. Our findings support a previously reported trend that rationalizes the observed lower bound in oxygen evolution (OER) overpotentials from correlations in OH* and OOH* adsorption energies. In addition, we report hydrogen adsorption energies that may be used to estimate hydrogenmore » evolution (HER) overpotentials along with potential metrics for electrochemical metastability in reducing environments. Finally, we also report and discuss trends between atom-projected density of states and adsorption energies, which may enable a design criteria from the local electronic structure of the active site.« less

Xe adsorption site distributions on Pt(111), Pt(221) and Pt(531)

NASA Astrophysics Data System (ADS)

Gellman, Andrew J.; Baker, L.; Holsclaw, B. S.

2016-04-01

The ideal structures of the Pt(111), Pt(221) and Pt(531) surfaces expose adsorption sites that can be qualitatively described as terrace sites on Pt(111), both step and terrace sites on Pt(221), and kink sites on Pt(531). The real surface structures of these surfaces can be complicated by imperfections such as misorientation, reconstruction and thermal roughening, all of which will influence their distributions of adsorption sites. Xe adsorption sites on the Pt(111), Pt(221) and Pt(531) surfaces have been probed using both photoemission of adsorbed Xe (PAX) and temperature programmed desorption (TPD) of Xe. Both PAX and Xe TPD are sensitive to the adsorption sites of the Xe and serve as complementary means of assessing the distributions of adsorption sites on these three Pt surfaces. The adsorption of Xe is sufficiently sensitive to detect the presence of residual steps on the Pt(111) surface at a density of 1.5% step atoms per Pt atom. On the Pt(221) surface, PAX and Xe TPD reveal adsorption at both terrace and step sites simultaneously. Although the ideal structure of the Pt(531) surface has no well-defined steps or terraces, Xe adsorption indicates that its adsorption sites are best described as a distribution of both step and kink sites with roughly twice as many steps sites as kinks.

Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

PubMed

Chayawan; Vikas

2016-11-01

This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Comparison of two strategies for detection of reactive oxygen species

NASA Astrophysics Data System (ADS)

Gao, Weidong; Zhou, Yuanshu; Gu, Yueqing

2014-09-01

Photodynamic therapy (PDT) is a clinically approved treatment that was applied to oncology , dermatology, and ophthalmology. Reactive oxygen species (ROS) play a important role in the efficacy of PDT. Online monitoring of reactive oxygen species is the key to understand effect of PDT treatment. We used Fluorescence probes DPBF and luminescent probe luminal to measure the ROS in cells. And we revaluate the relationship between the amount of light and cell survival. There is strongly correlated between the amount of light and cell kill.

Mesoporous zirconium titanium oxides. Part 1: Porosity modulation and adsorption properties of xerogels.

PubMed

Griffith, Christopher S; Sizgek, G Devlet; Sizgek, Erden; Scales, Nicholas; Yee, Patrick J; Luca, Vittorio

2008-11-04

A series of zirconium titanium oxide mesophases containing 33 atom % Zr have been prepared using carboxylic acids of different alkyl chain lengths (Cy ) from y=4-18 through organic-inorganic polymer phase segregation as the gel transition is approached. Thermal treatment of these transparent gels up to 450 degrees C eliminated the organic template, and domain coarsening occurred affording stable worm-hole mesoporous materials of homogeneous composition and pore diameters varying from about 3 to 4 nm in fine increments. With such materials, it was subsequently possible to precisely study the adsorption of vanadium oxo-anions and cations from aqueous solutions and, more particularly, probe the kinetics of intraparticle mass transport as a function of the associated pore dimension. The kinetics of mass transport through the pore systems was investigated using aqueous vanadyl (VO2+) and orthovanadate (VO3(OH)2-) probe species at concentrations ranging from 10 to 200 ppm (0.2 to 4 mmol/L) and pH values of 0 and 10.5, respectively. In the case of both of these vanadium species, the zirconium titanate mesophases displayed relatively slow kinetics, taking in excess of about 500 min to achieve maximum uptake. By using a pseudo-second-order rate law, it was possible to extract the instantaneous and overall rate of the adsorption processes and then relate these to the pore diameters. Both the instantaneous and overall rates of adsorption increased with increasing surface area and pore diameter over the studied pore size range. However, the equilibrium adsorption capacity increased linearly with pore diameter only for the higher concentrations and was independent of pore diameter for the lower concentration. These results have been interpreted using a model in which discrete adsorption occurs at low concentrations and is then followed by multilayer adsorption at higher concentration.

Morphology and Surface Reactivity Relationship in the Li1+xMn2-xO4 Spinel with x = 0.05 and 0.10: A Combined First-Principle and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Vallverdu, Germain; Flahaut, Delphine; Allouche, Joachim; Croguennec, Laurence; Ménétrier, Michel; Baraille, Isabelle

2017-12-27

This article focuses on the surface reactivity of two spinel samples with different stoichiometries and crystal morphologies, namely Li 1+x Mn 2-x O 4 with x = 0.05 and 0.10. LiMn 2 O 4 compounds are good candidates as positive electrode of high-power lithium-ion batteries for portable devices. The samples were investigated using both experimental and theoretical approaches. On the experimental point of view, they were characterized in depth from X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy (XPS) analyses. Then, the reactivity was investigated through the adsorption of (SO 2 ) gaseous probes, in controlled conditions, followed by XPS characterization. First-principle calculations were conducted simultaneously to investigate the electronic properties and the reactivity of relevant surfaces of an ideal LiMn 2 O 4 material. The results allow us to conclude that the reactivity of the samples is dominated by an acido-basic reactivity and the formation of sulfite species. Nonetheless, on the x = 0.05 sample, both sulfite and sulfate species are obtained, the later, in lesser extent, corresponding to a redox reactivity. Combining experimental and theoretical results, this redox reactivity could be associated with the presence of a larger quantity of Mn 4+ cations on the last surface layers of the material linked to a specific surface orientation.

A mitochondria-targeted turn-on fluorescent probe for the detection of glutathione in living cells.

PubMed

Zhang, Jian; Bao, Xiaolong; Zhou, Junliang; Peng, Fangfang; Ren, Hang; Dong, Xiaochun; Zhao, Weili

2016-11-15

A novel turn-on red fluorescent BODIPY-based probe (Probe 1) for the detection of glutathione was developed. Such a probe carries a para-dinitrophenoxy benzyl pyridinium moiety at the meso position of a BODIPY dye as self-immolative linker. Probe 1 responds selectively to glutathione with the detection limit of 109nM over other amino acids, common metal ions, reactive oxygen species, reactive nitrogen species, and reactive sulfur species. A novel electrostatic interaction to modulate the SNAr attack of glutathione was believed to play significant role for the observed selective response to glutathione. The cleavage of dinitrophenyl ether by glutathione leads to the production of para-hydroxybenzyl moiety which is able to self-immolate through an intramolecular 1,4-elimination reaction to release the fluorescent BODIPY dye. The low toxic probe has been successfully used to detect mitochondrial glutathione in living cells. Copyright © 2016 Elsevier B.V. All rights reserved.

Removal of nitric oxide by the highly reactive anatase TiO2 (001) surface: a density functional theory study.

PubMed

Zhao, Wenwen; Tian, Feng Hui; Wang, Xiaobin; Zhao, Linghuan; Wang, Yun; Fu, Aiping; Yuan, Shuping; Chu, Tianshu; Xia, Linhua; Yu, Jimmy C; Duan, Yunbo

2014-09-15

In this paper, density functional theory (DFT) calculation was employed to study the adsorption of nitric oxide (NO) on the highly reactive anatase TiO2 (001) surface. For comparison, the adsorption of NO on the (101) surface was also considered. Different from the physical adsorption on the (101) surface, NO molecules are found to chemisorb on the TiO2 (001) surface. The twofold coordinate oxygen atoms (O2c) on the anatase (001) surface are the active sites. Where NO is oxidized into a nitrite species (NO2(-)) trapping efficiently on the surface, with one of the surface Ti5c-O2c bonds adjacent to the adsorption site broken. Our results, therefore, supply a theoretical guidance to remove NO pollutants using highly reactive anatase TiO2 (001) facets. Copyright © 2014 Elsevier Inc. All rights reserved.

Effect of working power and pressure on plasma properties during the deposition of TiN films in reactive magnetron sputtering plasma measured using Langmuir probe measurement

NASA Astrophysics Data System (ADS)

How, Soo Ren; Nayan, Nafarizal; Khairul Ahmad, Mohd; Fhong Soon, Chin; Zainizan Sahdan, Mohd; Lias, Jais; Shuhaimi Abu Bakar, Ahmad; Arshad, Mohd Khairuddin Md; Hashim, Uda; Yazid Ahmad, Mohd

2018-04-01

The ion, electron density and electron temperature during formation of TiN films in reactive magnetron sputtering system have been investigated for various settings of radio frequency (RF) power and working pressure by using Langmuir probe measurements. The RF power and working pressure able to affect the densities and plasma properties during the deposition process. In this work, a working pressure (100 and 20 mTorr) and RF power (100, 150 and 200 W) have been used for data acquisition of probe measurement. Fundamental of studied on sputter deposition is very important for improvement of film quality and deposition rate. Higher working pressure and RF power able to produce a higher ion density and reduction of electron temperature.

Cell wall reactivity of acidophilic and alkaliphilic bacteria determined by potentiometric titrations and Cd adsorption experiments.

PubMed

Kenney, Janice P L; Fein, Jeremy B

2011-05-15

In this study, we used potentiometric titrations and Cd adsorption experiments to determine the binding capacities of two acidophilic (A. cryptum and A. acidophilum) and two alkaliphilic (B. pseudofirmus and B. circulans) bacterial species in order to determine if any consistent trends could be observed relating bacterial growth environment to proton and Cd binding properties and to compare those binding behaviors to those of neutrophilic bacteria. All of the bacterial species studied exhibited significant proton buffering over the pH range in this study, with the alkaliphiles exhibiting significantly higher acidity constants than the acidophiles as well as the neutrophilic bacterial consortia. The calculated average site concentrations for each of the bacteria in this study are within 2σ experimental error of each other, with the exception of A. cryptum, which has a significantly higher Site 2 concentration than the other species. Despite differing acidity constants between the acidophiles and alkaliphiles, all bacteria except A. cryptum exhibited remarkably similar Cd adsorption behavior to each other, and the observed extent of adsorption was also similar to that predicted from a generalized model derived using neutrophilic bacterial consortia. This study demonstrates that bacteria that grow under extreme conditions exhibit similar proton and metal adsorption behavior to that of previously studied neutrophilic species and that a single set of proton and metal binding constants can be used to model the behavior of bacterial adsorption under a wide range of environmental conditions.

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) as a probe of macromolecule adsorption kinetics at functionalized interfaces.

PubMed

O'Connell, Michael A; de Cuendias, Anne; Gayet, Florence; Shirley, Ian M; Mackenzie, Stuart R; Haddleton, David M; Unwin, Patrick R

2012-05-01

Evanescent wave cavity ring-down spectroscopy (EW-CRDS) has been employed to study the interfacial adsorption kinetics of coumarin-tagged macromolecules onto a range of functionalized planar surfaces. Such studies are valuable in designing polymers for complex systems where the degree of interaction between the polymer and surface needs to be tailored. Three tagged synthetic polymers with different functionalities are examined: poly(acrylic acid) (PAA), poly(3-sulfopropyl methacrylate, potassium salt) (PSPMA), and a mannose-modified glycopolymer. Adsorption transients at the silica/water interface are found to be characteristic for each polymer, and kinetics are deduced from the initial rates. The chemistry of the adsorption interfaces has been varied by, first, manipulation of silica surface chemistry via the bulk pH, followed by surfaces modified by poly(L-glutamic acid) (PGA) and cellulose, giving five chemically different surfaces. Complementary atomic force microscopy (AFM) imaging has been used for additional surface characterization of adsorbed layers and functionalized interfaces to allow adsorption rates to be interpreted more fully. Adsorption rates for PSPMA and the glycopolymer are seen to be highly surface sensitive, with significantly higher rates on cellulose-modified surfaces, whereas PAA shows a much smaller rate dependence on the nature of the adsorption surface.

Effect of lipophilization on the distribution and reactivity of ingredients in emulsions.

PubMed

Leong, Wai Fun; Berton-Carabin, Claire C; Elias, Ryan J; Lecomte, Jérôme; Villeneuve, Pierre; Zhao, Yu; Coupland, John N

2015-12-01

The reactivity of small molecules in emulsions is believed to depend on their partitioning between phases, yet this is hard to verify experimentally in situ. In the present work, we use electron paramagnetic resonance (EPR) spectroscopy to simultaneously measure the distribution and reactivity of a homologous series of lipophilized spin probes in an emulsion. 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPOL) was derivatized with saturated fatty acids to create a series of spin probes with increasing lipophilicity (C4-, C8-, C12-, and C16-TEMPO). The probes were added to a 10 wt.% tetradecane-in water emulsions (d32∼190 nm) stabilized with sodium caseinate (1 wt.% in the aqueous phase, pH 7). The distribution of the probes between phases was measured by electron paramagnetic resonance (EPR) spectroscopy. TEMPOL partitioned into the aqueous phase, C4-TEMPO distributed between the lipid and aqueous phases (69% and 31% respectively) while the more lipophilic probes dissolved exclusively within the lipid droplets. Interestingly, the more lipophilic probes initially precipitated upon their addition to the emulsion, and only slowly redistributed to the droplets over hours or days, the rate of which was dependent on their carbon chain length. The reactivity of the probes with aqueous an aqueous phase reductant (ascorbate) generally depended on the proportion in the aqueous phase (i.e., TEMPOL>C4-TEMPO>C8-TEMPO∼C12-TEMPO∼C16-TEMPO). Copyright © 2015 Elsevier Inc. All rights reserved.

LOCATION AND CHARACTERIZATION OF SUBSURFACE ANOMALIES USING A SOIL CONDUCTIVITY PROBE

EPA Science Inventory

An electrical conductivity probe, designed for use with "direct push" technology, has been successfully used to locate buried drums, contaminant plumes, and to precisely locate and characterize a previously installed permeable reactive iron wall. The conductivity probe was desig...

Adsorption of dyes by ACs prepared from waste tyre reinforcing fibre. Effect of texture, surface chemistry and pH.

PubMed

Acevedo, Beatriz; Rocha, Raquel P; Pereira, Manuel F R; Figueiredo, José L; Barriocanal, Carmen

2015-12-01

This paper compares the importance of the texture and surface chemistry of waste tyre activated carbons in the adsorption of commercial dyes. The adsorption of two commercial dyes, Basic Astrazon Yellow 7GLL and Reactive Rifafix Red 3BN on activated carbons made up of reinforcing fibres from tyre waste and low-rank bituminous coal was studied. The surface chemistry of activated carbons was modified by means of HCl-HNO3 treatment in order to increase the number of functional groups. Moreover, the influence of the pH on the process was also studied, this factor being of great importance due to the amphoteric characteristics of activated carbons. The activated carbons made with reinforcing fibre and coal had the highest SBET, but the reinforcing fibre activated carbon samples had the highest mesopore volume. The texture of the activated carbons was not modified upon acid oxidation treatment, unlike their surface chemistry which underwent considerable modification. The activated carbons made with a mixture of reinforcing fibre and coal experienced the largest degree of oxidation, and so had more acid surface groups. The adsorption of reactive dye was governed by the mesoporous volume, whilst surface chemistry played only a secondary role. However, the surface chemistry of the activated carbons and dispersive interactions played a key role in the adsorption of the basic dye. The adsorption of the reactive dye was more favored in a solution of pH 2, whereas the basic dye was adsorbed more easily in a solution of pH 12. Copyright © 2015 Elsevier Inc. All rights reserved.

Competitive adsorption of textile dyes using peat: adsorption equilibrium and kinetic studies in monosolute and bisolute systems.

PubMed

Sepulveda, L; Troncoso, F; Contreras, E; Palma, C

2008-09-01

The purpose of this study is to investigate the adsorption by peat of four reactive textile dyes with the following commercial names: Yellow CIBA WR 200% (Y), Dark Blue CIBA WR (DB), Navy CIBA WB (N), and Red CIBA WB 150% (R), used in a cotton-polyester fabric finishing plant. The decolorization levels obtained varied between 5% and 30%, and the most significant variables were pH and ionic strength. Equilibrium studies were carried out at pH 2.8 and temperature of 25 degrees C. Maximum adsorption capacities were between 15 and 20 mg g(-1). Experimental data were fitted to the models of Langmuir. The equilibrium studies for bisolute systems were DB-R and Y-N mixtures. The Langmuir extended model indicated that there is competition for adsorption sites and without interaction between dyes. The results of the kinetic adsorption studies on monosolute and bisolute systems were fitted to the film-pore diffusion, variable diffusivity and quasi-stationary models. They showed that the diffusivity coefficients obtained varied between 2.0 x 10(-8) and 8.5 x 10(-8) cm2s(-1) when the variable diffusivity mass transfer model (VDM) was used and effective diffusion coefficient was fitted between 3.3 x 10(-7) and 56.0 x 10(-7) cm2s(-1) for the film-pore diffusion model (FPDM). The root of average of squares relative error obtained varied between 0.8% and 47.0% for the VDM and FPDM models, respectively.

New method for evaluating irreversible adsorption and stationary phase bleed in gas chromatographic capillary columns.

PubMed

Wright, Bob W; Wright, Cherylyn W

2012-10-26

A novel method is described for the evaluation of irreversible adsorption and column bleed in gas chromatographic (GC) columns using a tandem GC approach. This work specifically determined the degree of irreversible adsorption behavior of specific sulfur and phosphorous containing test probe compounds at levels ranging from approximately 50 picograms (pg) to 1 nanogram (ng) on selected gas chromatographic columns. This method does not replace existing evaluation methods that characterize reversible adsorption but provides an additional tool. The test compounds were selected due to their ease of adsorption and their importance in the specific trace analytical detection methodology being developed. Replicate chromatographic columns with 5% phenylmethylpolysiloxane (PMS), polyethylene glycol (wax), trifluoropropylpolysiloxane (TFP), or 78% cyanopropylpolysiloxane stationary phases from a variety of vendors were evaluated. As expected, the results demonstrate that the different chromatographic phases exhibit differing degrees of irreversible adsorption behavior. The results also indicate that all manufacturers do not produce equally inert columns nor are columns from a given manufacturer identical. The wax-coated columns for the test probes used were more inert as a group than 5% PMS coated columns, and they were more reproducibly manufactured. Both TFP and 78% cyanopropylpolysiloxane columns displayed superior inertness to the test compounds compared to either 5% PMS- or wax-coated columns. Irreversible adsorption behavior was characterized for a limited range of stationary phase film thicknesses. In addition, the method was shown effective for characterizing column bleed and methods to remove bleed components. This method is useful in screening columns for demanding applications and to obtain diagnostic information related to improved preparation methods. Copyright © 2012 Elsevier B.V. All rights reserved.

Heavy metal removal capacity of individual components of permeable reactive concrete

NASA Astrophysics Data System (ADS)

Holmes, Ryan R.; Hart, Megan L.; Kevern, John T.

2017-01-01

Permeable reactive barriers (PRBs) are a well-known technique for groundwater remediation using industrialized reactive media such as zero-valent iron and activated carbon. Permeable reactive concrete (PRC) is an alternative reactive medium composed of relatively inexpensive materials such as cement and aggregate. A variety of multimodal, simultaneous processes drive remediation of metals from contaminated groundwater within PRC systems due to the complex heterogeneous matrix formed during cement hydration. This research investigated the influence coarse aggregate, portland cement, fly ash, and various combinations had on the removal of lead, cadmium, and zinc in solution. Absorption, adsorption, precipitation, co-precipitation, and internal diffusion of the metals are common mechanisms of removal in the hydrated cement matrix and independent of the aggregate. Local aggregates can be used as the permeable structure also possessing high metal removal capabilities, however calcareous sources of aggregate are preferred due to improved removal with low leachability. Individual adsorption isotherms were linear or curvilinear up, indicating a preferred removal process. For PRC samples, metal saturation was not reached over the range of concentrations tested. Results were then used to compare removal against activated carbon and aggregate-based PRBs by estimating material costs for the remediation of an example heavy metal contaminated Superfund site located in the Midwestern United States, Joplin, Missouri.

Adsorption and covalent binding of fibrinogen as a method for probing the chemical composition of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microsphere surfaces.

PubMed

Gosecka, Monika; Chehimi, Mohamed M; Basinska, Teresa; Slomkowski, Stanislaw; Makowski, Tomasz

2017-12-01

We investigated the distribution of polyglycidol and polystyrene on the surface of poly(styrene/α-tert-butoxy-ω-vinylbenzyl-polyglycidol) microspheres (random distribution or segregated into hydrophilic and hydrophobic patches), using fibrinogen (Fb) as a macromolecular probe. The fibrinogen was adsorbed or covalently attached to the surface of the poly(styrene-co-α-tert-butoxy-ω-vinylbenzyl-polyglycidol) (P(S/PGLy)) microspheres. The P(S/PGLy) particles were prepared by emulsion copolymerization of styrene and α-tert-butoxy-ω-vinylbenzyl-polyglycidol (PGLy) macromonomer initiated with potassium persulfate. The polymerizations yielded P(S/PGLy) particles with various surface fractions of polyglycidol, depending on the amount of added macromonomer and the addition process. In some syntheses, the entire macromonomer amount was added once at the beginning of the polymerization, while in others, the macromonomer was added gradually after the formation of particle seeds from pure polystyrene. XPS studies revealed that the fraction of polyglycidol in the interfacial layer of the microspheres was larger when the entire amount of macromonomer was added at the beginning of the polymerization than when it was added after formation of the polystyrene seeds. Studies of fibrinogen adsorption provided the first evidence of segregation of the hydrophobic (polystyrene) and hydrophilic (polyglycidol) components at the surface of the composite P(S/PGLy) microspheres into patches. The hydrophobic patches are composed mainly of polystyrene. However, they also contain a small amount of polyglycidol chains, making the adsorption of fibrinogen weaker than the adsorption onto the pure polystyrene. Studies of covalent immobilization of fibrinogen on the microspheres via 1,3,5-trichlorotriazine confirmed these findings. Copyright © 2017 Elsevier B.V. All rights reserved.

Complexation-Based Detection of Nickel(II) at a Graphene-Chelate Probe in the Presence of Cobalt and Zinc by Adsorptive Stripping Voltammetry

PubMed Central

Pokpas, Keagan; Jahed, Nazeem; Baker, Priscilla G.

2017-01-01

The adsorptive stripping voltammetric detection of nickel and cobalt in water samples at metal film electrodes has been extensively studied. In this work, a novel, environmentally friendly, metal-free electrochemical probe was constructed for the ultra-trace determination of Ni2+ in water samples by Adsorptive Cathodic Stripping Voltammetry (AdCSV). The electrochemical platform is based on the adsorptive accumulation of Ni2+ ions directly onto a glassy carbon electrode (GCE) modified with dimethylglyoxime (DMG) as chelating agent and a Nafion-graphene (NGr) nanocomposite to enhance electrode sensitivity. The nafion-graphene dimethylglyoxime modified glassy carbon electrode (NGr-DMG-GCE) shows superior detection capabilities as a result of the improved surface-area-to-volume ratio and enhanced electron transfer kinetics following the incorporation of single layer graphene, while limiting the toxic effects of the sensor by removal of the more common mercury, bismuth and lead films. Furthermore, for the first time the NGr-DMG-GCE, in the presence of common interfering metal ions of Co2+ and Zn2+ demonstrates good selectivity and preferential binding towards the detection of Ni2+ in water samples. Structural and morphological characterisation of the synthesised single layer graphene sheets was conducted by Raman spectrometry, HRTEM and HRSEM analysis. The instrumental parameters associated with the electrochemical response, including accumulation potential and accumulation time were investigated and optimised in addition to the influence of DMG and graphene concentrations. The NGr-DMG-GCE demonstrated well resolved, reproducible peaks, with RSD (%) below 5% and a detection limit of 1.5 µg L−1 for Ni2+ reduction at an accumulation time of 120 s. The prepared electrochemical sensor exhibited good detection and quantitation towards Ni2+ detection in tap water samples, well below 0.1 mg L−1 set by the WHO and EPA standards. This is comparable to the South African

Factors affecting the removal of ammonia from air on carbonaceous materials: Investigation of reactive adsorption mechanism

NASA Astrophysics Data System (ADS)

Petit, Camille

Air pollution related to the release of industrial toxic gases, represents one of the main concerns of our modern world owing to its detrimental effect on the environment. To tackle this growing issue, efficient ways to reduce/control the release of pollutants are required. Adsorption of gases on porous materials appears as a potential solution. However, the physisorption of small molecules of gases such as ammonia is limited at ambient conditions. For their removal, adsorbents providing strong adsorption forces must be used/developed. In this study, new carbon-based materials are prepared and tested for ammonia adsorption at ambient conditions. Characterization of the adsorbents' texture and surface chemistry is performed before and after exposure to ammonia to identify the features responsible for high adsorption capacity and for controlling the mechanisms of retention. The characterization techniques include: nitrogen adsorption, thermal analysis, potentiometric titration, FT-IR spectroscopy, X-ray diffraction, Energy Dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and Electron Microscopy. The results obtained indicate that ammonia removal is governed by the adsorbent's surface chemistry. On the contrary, porosity (and thus physisorption) plays a secondary role in this process, unless strong dispersive forces are provided by the adsorbent. The surface chemistry features responsible for the enhanced ammonia adsorption include the presence of oxygen-(carboxyl, hydroxyl, epoxy) and sulfur- (sulfonic) containing groups. Metallic species improve the breakthrough capacity as well as they lead to the formation of Lewis acid-base interactions, hydrogen-bonding or complexation. In addition to the latter three mechanisms, ammonia is retained on the adsorbent surface via Bronsted acid-base interactions or via specific reactions with the adsorbent's functionalities leading to the incorporation of ammonia into the adsorbent's matrix. Another mechanism

Adsorption and desorption of arsenic to aquifer sediment on the Red River floodplain at Nam Du, Vietnam

PubMed Central

Thi Hoa Mai, Nguyen; Postma, Dieke; Thi Kim Trang, Pham; Jessen, Søren; Hung Viet, Pham; Larsen, Flemming

2016-01-01

The adsorption of arsenic onto aquifer sediment from the Red River floodplain, Vietnam, was determined in a series of batch experiments. Due to water supply pumping, river water infiltrates into the aquifer at the field site and has leached the uppermost aquifer sediments. The leached sediments, remain anoxic but contain little reactive arsenic and iron, and are used in our experiments. The adsorption and desorption experiments were carried out by addition or removal of arsenic from the aqueous phase in sediment suspensions under strictly anoxic conditions. Also the effects of HCO3, Fe(II), PO4 and Si on arsenic adsorption were explored. The results show much stronger adsorption of As(V) as compared to As(III), full reversibility for As(III) adsorption and less so for As(V). The presence or absence of HCO3 did not influence arsenic adsorption. Fe(II) enhanced As(V) sorption but did not influence the adsorption of As(III) in any way. During simultaneous adsorption of As(III) and Fe(II), As(III) was found to be fully desorbable while Fe(II) was completely irreversibly adsorbed and clearly the two sorption processes are uncoupled. Phosphate was the only solute that significantly could displace As(III) from the sediment surface. Compiling literature data on arsenic adsorption to aquifer sediment in Vietnam and Bangladesh revealed As(III) isotherms to be almost identical regardless of the nature of the sediment or the site of sampling. In contrast, there was a large variation in As(V) adsorption isotherms between studies. A tentative conclusion is that As(III) and As(V) are not adsorbing onto the same sediment surface sites. The adsorption behavior of arsenic onto aquifer sediments and synthetic Fe-oxides is compared. Particularly, the much stronger adsorption of As(V) than of As(III) onto Red River as well as on most Bangladesh aquifer sediments, indicates that the perception that arsenic, phosphate and other species compete for the same surface sites of iron oxides in

Adsorption and Desulfurization Mechanism of Thiophene on Layered FeS(001), (011), and (111) Surfaces: A Dispersion-Corrected Density Functional Theory Study

PubMed Central

2017-01-01

Layered transition-metal chalcogenides have emerged as a fascinating new class of materials for catalysis. Here, we present periodic density functional theory (DFT) calculations of the adsorption of thiophene and the direct desulfurization reaction pathways on the (001), (011), and (111) surfaces of layered FeS. The fundamental aspects of the thiophene adsorption, including the initial adsorption geometries, adsorption energies, structural parameters, and electronic properties, are presented. From the calculated adsorption energies, we show that the flat adsorption geometries, wherein the thiophene molecule forms multiple π-bonds with the FeS surfaces, are energetically more favorable than the upright adsorption geometries, with the strength of adsorption decreasing in the order FeS(111) > FeS(011) > FeS(001). The adsorption of the thiophene onto the reactive (011) and (111) surfaces is shown to be characterized by charge transfer from the interacting Fe d-band to the π-system of the thiophene molecule, which causes changes of the intramolecular structure including loss of aromaticity and elongation of the C–S bonds. The thermodynamic and kinetic analysis of the elementary steps involved in the direct desulfurization of thiophene on the reactive FeS surfaces is also presented. Direct desulfurization of thiophene occurs preferentially on the (111) surface, as reflected by the overall exothermic reaction energy calculated for the process (ER = −0.15 eV), with an activation energy of 1.58 eV. PMID:29348782

SPM analysis of fibrinogen adsorption on solid surfaces

NASA Astrophysics Data System (ADS)

Choukourov, A.; Grinevich, A.; Saito, N.; Takai, O.

2007-09-01

The adsorption kinetics, adhesion and orientation of human fibrinogen on solid surfaces have been studied by surface probe microscopy (SPM) and quartz crystal microbalance techniques (QCM). CF 3-, NH 2-terminated organo-silane self-assembled monolayers (SAM) and OH-terminated silicon dioxide have been used as model surfaces. Furthermore, the interaction of fibrinogen with nanocomposite Ti/hydrocarbon plasma polymer films (Ti/ppCH) deposited by dc magnetron sputtering has also been studied.

On the Adsorption of DNA Origami Nanostructures in Nanohole Arrays.

PubMed

Brassat, Katharina; Ramakrishnan, Saminathan; Bürger, Julius; Hanke, Marcel; Doostdar, Mahnaz; Lindner, Jörg K N; Grundmeier, Guido; Keller, Adrian

2018-05-22

DNA origami nanostructures are versatile substrates for the controlled arrangement of molecular capture sites with nanometer precision and thus have many promising applications in single-molecule bioanalysis. Here, we investigate the adsorption of DNA origami nanostructures in nanohole arrays which represent an important class of biosensors and may benefit from the incorporation of DNA origami-based molecular probes. Nanoholes with well-defined diameter that enable the adsorption of single DNA origami triangles are fabricated in Au films on Si wafers by nanosphere lithography. The efficiency of directed DNA origami adsorption on the exposed SiO 2 areas at the bottoms of the nanoholes is evaluated in dependence of various parameters, i.e., Mg 2+ and DNA origami concentrations, buffer strength, adsorption time, and nanohole diameter. We observe that the buffer strength has a surprisingly strong effect on DNA origami adsorption in the nanoholes and that multiple DNA origami triangles with 120 nm edge length can adsorb in nanoholes as small as 120 nm in diameter. We attribute the latter observation to the low lateral mobility of once adsorbed DNA origami on the SiO 2 surface, in combination with parasitic adsorption to the Au film. Although parasitic adsorption can be suppressed by modifying the Au film with a hydrophobic self-assembled monolayer, the limited surface mobility of the adsorbed DNA origami still leads to poor localization accuracy in the nanoholes and results in many DNA origami crossing the boundary to the Au film even under optimized conditions. We discuss possible ways to minimize this effect by varying the composition of the adsorption buffer, employing different fabrication conditions, or using other substrate materials for nanohole array fabrication.

Chemical modeling of boron adsorption by humic materials using the constant capacitance model

USDA-ARS?s Scientific Manuscript database

The constant capacitance surface complexation model was used to describe B adsorption behavior on reference Aldrich humic acid, humic acids from various soil environments, and dissolved organic matter extracted from sewage effluents. The reactive surface functional groups on the humic materials wer...

Surface adsorption and hopping cause probe-size-dependent microrheology of actin networks

NASA Astrophysics Data System (ADS)

He, Jun; Tang, Jay X.

2011-04-01

A network of filaments formed primarily by the abundant cytoskeletal protein actin gives animal cells their shape and elasticity. The rheological properties of reconstituted actin networks have been studied by tracking micron-sized probe beads embedded within the networks. We investigate how microrheology depends on surface properties of probe particles by varying the stickiness of their surface. For this purpose, we chose carboxylate polystyrene (PS) beads, silica beads, bovine serum albumin (BSA) -coated PS beads, and polyethylene glycol (PEG) -grafted PS beads, which show descending stickiness to actin filaments, characterized by confocal imaging and microrheology. Probe size dependence of microrheology is observed for all four types of beads. For the slippery PEG beads, particle-tracking microrheology detects weaker networks using smaller beads, which tend to diffuse through the network by hopping from one confinement “cage” to another. This trend is reversed for the other three types of beads, for which microrheology measures stiffer networks for smaller beads due to physisorption of nearby filaments to the bead surface. We explain the probe size dependence with two simple models. We also evaluate depletion effect near nonadsorption bead surface using quantitative image analysis and discuss the possible impact of depletion on microrheology. Analysis of these effects is necessary in order to accurately define the actin network rheology both in vitro and in vivo.

Adsorption site analysis of impurity embedded single-walled carbon nanotube bundles

USGS Publications Warehouse

Agnihotri, S.; Mota, J.P.B.; Rostam-Abadi, M.; Rood, M.J.

2006-01-01

Bundle morphology and adsorptive contributions from nanotubes and impurities are studied both experimentally and by simulation using a computer-aided methodology, which employs a small physisorbed probe molecule to explore the porosity of nanotube samples. Grand canonical Monte Carlo simulation of nitrogen adsorption on localized sites of a bundle is carried out to predict adsorption in its accessible internal pore volume and on its external surface as a function of tube diameter. External adsorption is split into the contributions from the clean surface of the outermost nanotubes of the bundle and from the surface of the impurities. The site-specific isotherms are then combined into a global isotherm for a given sample using knowledge of its tube-diameter distribution obtained by Raman spectroscopy. The structural parameters of the sample, such as the fraction of open-ended nanotubes and the contributions from impurities and nanotube bundles to total external surface area, are determined by fitting the experimental nitrogen adsorption data to the simulated isotherm. The degree of closure between experimental and calculated adsorption isotherms for samples manufactured by two different methods, to provide different nanotube morphology and contamination level, further strengthens the validity and resulting interpretations based on the proposed approach. The average number of nanotubes per bundle and average bundle size, within a sample, are also quantified. The proposed method allows for extrapolation of adsorption properties to conditions where the purification process is 100% effective at removing all impurities and opening access to all intrabundle adsorption sites. ?? 2006 Elsevier Ltd. All rights reserved.

BSA adsorption onto nanospheres: Influence of surface curvature as probed by electrophoretic light scattering and UV/vis spectroscopy

NASA Astrophysics Data System (ADS)

Sánchez-Pérez, Julio A.; Gallardo-Moreno, Amparo M.; González-Martín, M. Luisa; Vadillo-Rodríguez, Virginia

2015-10-01

The influence of surface curvature on the adsorption of bovine serum albumin (BSA) was evaluated through the combination of two fairly simple techniques: electrophoretic light scattering and UV/vis spectroscopy. Measurements were carried out for a range of protein concentrations (0-320 μg/ml) at pH 3.5, 4.5 and 7 using hydrophobic polystyrene nanospheres of 38.8, 82 and 220 nm in diameter. The results obtained demonstrate that the charge of the BSA molecules in solution dictates the pH-dependent behavior of the protein-coated nanospheres, indicating in all cases a significant adsorption of BSA molecules. At a fixed pH, however, it is the zeta potential that characterizes the uncoated nanospheres normalized by their surface area that primarily controls protein adsorption. In particular, it is found that the rate at which BSA interact with the different nanospheres increases as their negative zeta potential per unit area (or diameter) increases (decreases) regardless of the pH. Moreover, provided that adsorption occurs away from the isoelectric point of the protein, highly curved surfaces are found to stabilize the native-like conformation of BSA upon adsorption by likely reducing lateral interactions between adsorbed molecules.

Preferable adsorption of phosphate using lanthanum-incorporated porous zeolite: Characteristics and mechanism

NASA Astrophysics Data System (ADS)

He, Yinhai; Lin, Hai; Dong, Yingbo; Wang, Liang

2017-12-01

The adsorbent, where lanthanum oxide was incorporated onto porous zeolite (La-Z), of preferable adsorption towards phosphate was prepared by hydrothermal synthesis. Based on pH effect results, La-Z would effectively sequestrate phosphate over wider pH range of 3.0-7.0, alkaline conditions were unfavorable for phosphate. The adsorption of phosphate was not significantly influenced by ionic strength and by coexisting anions of chloride, nitrate and sulfate but bicarbonate showed slightly greater negative effects, indicating La-Z possessed highly selectivity to phosphate. Adsorption of phosphate could be well fitted by pseudo-second-order model and the process was mainly controlled by intra-particle diffusion. Equilibrium adsorption demonstrated that Langmuir model was more suitable than Freundlich model for description phosphate adsorption and the adsorption capacity was 17.2 mg P g-1, which exhibited 95% utilization of incorporated La. Over 95% phosphate was eliminated in real effluent treatment when the dose was 2 g L-1. The underlying mechanism for phosphate capture was probed with Zeta potential and X-ray photoelectron spectroscope analysis, and the formation of La-P inner-sphere complexation was testified to be the dominant pathway. All the results suggested that the porous zeolite-supported lanthanum oxide can serve as a promising adsorbent for phosphate removal in realistic application.

Sugarcane bagasse powder as biosorbent for reactive red 120 removals from aqueous solution

NASA Astrophysics Data System (ADS)

Ahmad, S.; Wong, Y. C.; Veloo, K. V.

2018-04-01

Reactive red 120 is used as a textile dye for fabric coloring. The dye waste is produced during textile finishing process subsequently released directly to water bodies which giving harmful effects to the environment due to the carcinogenic characteristic. Adsorption process becomes an effective treatment to treat textile dye. This research emphasizes the treatment of textile dye namely reactive red 120 (RR120) by using sugarcane bagasse powder. The batch study was carried out under varying parameters such as 60 minutes contact time, pH (1-8), dye concentration (5-25 mg/L), particle size (125-500 μm) and biosorbent dosage (0.01-0.2 g/L). The maximum adsorption percentage of RR120 was 94.62%. The adsorption of dye was increased with the decreasing of pH, initial dye concentration and particle size. Sugarcane bagasse powder as low-cost biosorbent was established using Fourier Transform Infrared (FTIR) and scanning electron microscopy (SEM). This locally agricultural waste could be upgraded into useful material which is biosorbent that promising for decolorization of colored textile wastewater.

Template-directed synthesis and selective adsorption of oligoadenylates in hydroxyapatite

NASA Technical Reports Server (NTRS)

Gibbs, D.; Lohrmann, R.; Orgel, L. E.

1980-01-01

Polyuridylic acid is adsorbed completely from aqueous solution by hydroxyapatite under conditions that permit template-directed synthesis of oligoadenylates in free solution. The yield of oligoadenylates is enhanced to almost the same extent by poly(U) in the presence or the absence of hydroxyapatite. Under very similar conditions small quantities of hydroxyapatite adsorb higher-molecular-weight oligoadenylates selectively from a mixture of oligomers. On the basis of these results a mechanism for prebiotic oligonucleotide formation is proposed in which selective adsorption on hydroxyapatite or some other immobilized anion-exchanging material plays a major role. Monomers are released from the surface for reactivation, while oligomers are retained in a protected environment by adsorption to the apatite surface.

[Comparison study on adsorption of middle molecular substances with multiwalled carbon nanotubes and activated carbon].

PubMed

Li, Guifeng; Wan, Jianxin; Huang, Xiangqian; Zeng, Qiao; Tang, Jing

2011-08-01

In recent years, multi-walled carbon nanotubes (MWCTs) are very favorable to the adsorption of middle molecular substances in the hemoperfusion because of their multiporous structure, large surface area and high reactivity, which are beneficial to the excellent absorption properties. The purpose of this study was to study the MWCTs on the adsorption capacity of the middle molecular substances. Vitamin B12 (VB12) was selected as a model of the middle molecular substances. The morphologies of MWCTs and activated carbon from commercial "carbon kidney" were observed with scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The adsorption behavior of VB12 was compared to each other with UV-visible absorption spectra. The MWCTs formed a sophistaicate gap structure, and compared to the activated carbon, MWCTs had a larger surface area. By Langmuir equation and Freundlich equation fitting analysis, VB12 adsorption on MWCTs is fit for multi-molecular layer adsorption, and the adsorption type of activated carbon is more inclined to the model corresponding to Langmuir monolayer adsorption. The adsorption rate of MWCTs is faster than that of the activated carbon and the adsorption capacity is greater, which could be expected to become the new adsorbent in the hemoperfusion.

Doping as a means to probe the potential dependence of dopamine adsorption on carbon-based surfaces: A first-principles study

NASA Astrophysics Data System (ADS)

Aarva, Anja; Laurila, Tomi; Caro, Miguel A.

2017-06-01

In this work, we study the adsorption characteristics of dopamine (DA), ascorbic acid (AA), and dopaminequinone (DAox) on carbonaceous electrodes. Our goal is to obtain a better understanding of the adsorption behavior of these analytes in order to promote the development of new carbon-based electrode materials for sensitive and selective detection of dopamine in vivo. Here we employ density functional theory-based simulations to reach a level of detail that cannot be achieved experimentally. To get a broader understanding of carbonaceous surfaces with different morphological characteristics, we compare three materials: graphene, diamond, and amorphous carbon (a-C). Effects of solvation on adsorption characteristics are taken into account via a continuum solvent model. Potential changes that take place during electrochemical measurements, such as cyclic voltammetry, can also alter the adsorption behavior. In this study, we have utilized doping as an indirect method to simulate these changes by shifting the work function of the electrode material. We demonstrate that sp2- and sp3-rich materials, as well as a-C, respond markedly different to doping. Also the adsorption behavior of the molecules studied here differs depending on the surface material and the change in the surface potential. In all cases, adsorption is spontaneous, but covalent bonding is not detected in vacuum. The aqueous medium has a large effect on the adsorption behavior of DAox, which reaches its highest adsorption energy on diamond when the potential is shifted to more negative values. In all cases, inclusion of the solvent enhances the charge transfer between the slab and DAox. Largest differences in adsorption energy between DA and AA are obtained on graphene. Gaining better understanding of the behavior of the different forms of carbon when used as electrode materials provides a means to rationalize the observed complex phenomena taking place at the electrodes during electrochemical oxidation

Adsorption in zeolites using mechanically embedded ONIOM clusters

DOE PAGES

Patet, Ryan E.; Caratzoulas, Stavros; Vlachos, Dionisios G.

2016-09-01

Here, we have explored mechanically embedded three-layer QM/QM/MM ONIOM models for computational studies of binding in Al-substituted zeolites. In all the models considered, the high-level-theory layer consists of the adsorbate molecule and of the framework atoms within the first two coordination spheres of the Al atom and is treated at the M06-2X/6-311G(2df,p) level. For simplicity, flexibility and routine applicability, the outer, low-level-theory layer is treated with the UFF. We have modelled the intermediate-level layer quantum mechanically and investigated the performance of HF theory and of three DFT functionals, B3LYP, M06-2X and ωB97x-D, for different layer sizes and various basis sets,more » with and without BSSE corrections. We have studied the binding of sixteen probe molecules in H-MFI and compared the computed adsorption enthalpies with published experimental data. We have demonstrated that HF and B3LYP are inadequate for the description of the interactions between the probe molecules and the framework surrounding the metal site of the zeolite on account of their inability to capture dispersion forces. Both M06-2X and ωB97x-D on average converge within ca. 10% of the experimental values. We have further demonstrated transferability of the approach by computing the binding enthalpies of n-alkanes (C1–C8) in H-MFI, H-BEA and H-FAU, with very satisfactory agreement with experiment. The computed entropies of adsorption of n-alkanes in H-MFI are also found to be in good agreement with experimental data. Finally, we compare with published adsorption energies calculated by periodic-DFT for n-C3 to n-C6 alkanes, water and methanol in H-ZSM-5 and find very good agreement.« less

Probing Nanoparticle Reactivity at the Single-Molecule Level

DTIC Science & Technology

2014-02-15

nanorod hetero - nuclear particle (top) and a bime- tallic nanorod with two metal components (bottom). Both sys- tems have a metal-metal junction . Au...catalysts for co oxidation . J Am Chem Soc 133, 1978–1986 (2011). 32 F. Liu, J. Y. Lee & W. Zhou. Template preparation of multisegment ptni nanorods as...reactivity at nanoscale metal?metal junctions . (a) Papers published in peer-reviewed journals (N/A for none) Enter List of papers submitted or

Dissociative adsorption of O2 on unreconstructed metal (100) surfaces: Pathways, energetics, and sticking kinetics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Da-Jiang; Evans, James W.

An accurate description of oxygen dissociation pathways and kinetics for various local adlayer environments is key for an understanding not just of the coverage dependence of oxygen sticking, but also of reactive steady states in oxidation reactions. Density functional theory analysis for M(100) surfaces with M=Pd, Rh, and Ni, where O prefers the fourfold hollow adsorption site, does not support the traditional Brundle-Behm-Barker picture of dissociative adsorption onto second-nearest-neighbor hollow sites with an additional blocking constraint. Rather adsorption via neighboring vicinal bridge sites dominates, although other pathways can be active. The same conclusion also applies for M=Pt and Ir, wheremore » oxygen prefers the bridge adsorption site. Statistical mechanical analysis is performed based on kinetic Monte Carlo simulation of a multisite lattice-gas model consistent with our revised picture of adsorption. This analysis determines the coverage and temperature dependence of sticking for a realistic treatment of the oxygen adlayer structure.« less

Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species

NASA Astrophysics Data System (ADS)

Needham, Lisa-Maria; Weber, Judith; Fyfe, James W. B.; Kabia, Omaru M.; Do, Dung T.; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M.; Ghandi, Sonia; Bohndiek, Sarah E.; Snaddon, Thomas N.; Lee, Steven F.

2018-02-01

Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H2O2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H2O2. We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H2O2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species.

PubMed

Needham, Lisa-Maria; Weber, Judith; Fyfe, James W B; Kabia, Omaru M; Do, Dung T; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M; Ghandi, Sonia; Bohndiek, Sarah E; Snaddon, Thomas N; Lee, Steven F

2018-02-01

Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H 2 O 2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H 2 O 2 . We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H 2 O 2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease.

Reactivity of Nucleic Acid Radicals

PubMed Central

Greenberg, Marc M.

2016-01-01

Nucleic acid oxidation plays a vital role in the etiology and treatment of diseases, as well as aging. Reagents that oxidize nucleic acids are also useful probes of the biopolymers’ structure and folding. Radiation scientists have contributed greatly to our understanding of nucleic acid oxidation using a variety of techniques. During the past two decades organic chemists have applied the tools of synthetic and mechanistic chemistry to independently generate and study the reactive intermediates produced by ionizing radiation and other nucleic acid damaging agents. This approach has facilitated resolving mechanistic controversies and lead to the discovery of new reactive processes. PMID:28529390

Boronate-Based Fluorescent Probes: Imaging Hydrogen Peroxide in Living Systems

PubMed Central

Lin, Vivian S.; Dickinson, Bryan C.; Chang, Christopher J.

2014-01-01

Hydrogen peroxide, a reactive oxygen species with unique chemical properties, is produced endogenously in living systems as a destructive oxidant to ward off pathogens or as a finely tuned second messenger in dynamic cellular signaling pathways. In order to understand the complex roles that hydrogen peroxide can play in biological systems, new tools to monitor hydrogen peroxide in its native settings, with high selectivity and sensitivity, are needed. Knowledge of organic synthetic reactivity provides the foundation for the molecular design of selective, functional hydrogen peroxide probes. A palette of fluorescent and luminescent probes that react chemoselectively with hydrogen peroxide has been developed, utilizing a boronate oxidation trigger. These indicators offer a variety of colors and in cellulo characteristics and have been used to examine hydrogen peroxide in a number of experimental setups, including in vitro fluorometry, confocal fluorescence microscopy, and flow cytometry. In this chapter, we provide an overview of the chemical features of these probes and information on their behavior to help researchers select the optimal probe and application. PMID:23791092

Adsorption of dyes using different types of clay: a review

NASA Astrophysics Data System (ADS)

Adeyemo, Aderonke Ajibola; Adeoye, Idowu Olatunbosun; Bello, Olugbenga Solomon

2017-05-01

Increasing amount of dyes in the ecosystem particularly in wastewater has propelled the search for more efficient low-cost adsorbents. The effective use of the sorption properties (high surface area and surface chemistry, lack of toxicity and potential for ion exchange) of different clays as adsorbents for the removal of different type of dyes (basic, acidic, reactive) from water and wastewater as potential alternatives to activated carbons has recently received widespread attention because of the environmental-friendly nature of clay materials. Insights into the efficiencies of raw and modified/activated clay adsorbents and ways of improving their efficiencies to obtain better results are discussed. Acid-modified clay resulted in higher rate of dye adsorption and an increased surface area and porosity (49.05 mm2 and 53.4 %). Base-modified clay has lower adsorption capacities, while ZnCl2-modified clay had the least rate of adsorption with a surface area of 44.3 mm2 and porosity of 43.4 %. This review also explores the grey areas of the adsorption properties of the raw clays and the improved performance of activated/modified clay materials with particular reference to the effects of pH, temperature, initial dye concentration and adsorbent dosage on the adsorption capacities of the clays. Various challenges encountered in using clay materials are highlighted and a number of future prospects for the adsorbents are proposed.

Kinetic and Conformational Insights of Protein Adsorption onto Montmorillonite Revealed Using in Situ ATR-FTIR/2D-COS.

PubMed

Schmidt, Michael P; Martínez, Carmen Enid

2016-08-09

Protein adsorption onto clay minerals is a process with wide-ranging impacts on the environmental cycling of nutrients and contaminants. This process is influenced by kinetic and conformational factors that are often challenging to probe in situ. This study represents an in situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic investigation of the adsorption of a model protein (bovine serum albumin (BSA)) onto a clay mineral (montmorillonite) at four concentrations (1.50, 3.75, 7.50, and 15.0 μM) under environmentally relevant conditions. At all concentrations probed, FTIR spectra show that BSA readily adsorbs onto montmorillonite. Adsorption kinetics follow an Elovich model, suggesting that primary limitations on adsorption rates are surface-related heterogeneous energetic restrictions associated with protein rearrangement and lateral protein-protein interaction. BSA adsorption onto montmorillonite fits the Langmuir model, yielding K = 5.97 × 10(5) M(-1). Deconvolution and curve fitting of the amide I band at the end of the adsorption process (∼120 min) shows a large extent of BSA unfolding upon adsorption at 1.50 μM, with extended chains and turns increasing at the expense of α-helices. At higher concentrations/surface coverages, BSA unfolding is less pronounced and a more compact structure is assumed. Two-dimensional correlation spectroscopic (2D-COS) analysis reveals three different pathways corresponding to adsorbed conformations. At 1.50 μM, adsorption increases extended chains, followed by a loss in α-helices and a subsequent increase in turns. At 3.75 μM, extended chains decrease and then aggregated strands increase and side chains decrease, followed by a decrease in turns. With 7.50 and 15.0 μM BSA, the loss of side-chain vibrations is followed by an increase in aggregated strands and a subsequent decrease in turns and extended chains. Overall, the BSA concentration and resultant surface coverage have a profound

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.

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.

Bifunctional fluorescent probes for detection of amyloid aggregates and reactive oxygen species

PubMed Central

Needham, Lisa-Maria; Weber, Judith; Fyfe, James W. B.; Kabia, Omaru M.; Do, Dung T.; Klimont, Ewa; Zhang, Yu; Rodrigues, Margarida; Dobson, Christopher M.; Ghandi, Sonia; Bohndiek, Sarah E.; Snaddon, Thomas N.

2018-01-01

Protein aggregation into amyloid deposits and oxidative stress are key features of many neurodegenerative disorders including Parkinson's and Alzheimer's disease. We report here the creation of four highly sensitive bifunctional fluorescent probes, capable of H2O2 and/or amyloid aggregate detection. These bifunctional sensors use a benzothiazole core for amyloid localization and boronic ester oxidation to specifically detect H2O2. We characterized the optical properties of these probes using both bulk fluorescence measurements and single-aggregate fluorescence imaging, and quantify changes in their fluorescence properties upon addition of amyloid aggregates of α-synuclein and pathophysiological H2O2 concentrations. Our results indicate these new probes will be useful to detect and monitor neurodegenerative disease. PMID:29515860

Physiological and pathophysiological reactive oxygen species as probed by EPR spectroscopy: the underutilized research window on muscle ageing.

PubMed

A Abdel-Rahman, Engy; Mahmoud, Ali M; Khalifa, Abdulrahman M; Ali, Sameh S

2016-08-15

Reactive oxygen and nitrogen species (ROS and RNS) play crucial roles in triggering, mediating and regulating physiological and pathophysiological signal transduction pathways within the cell. Within the cell, ROS efflux is firmly controlled both spatially and temporally, making the study of ROS dynamics a challenging task. Different approaches have been developed for ROS assessment; however, many of these assays are not capable of direct identification or determination of subcellular localization of different ROS. Here we highlight electron paramagnetic resonance (EPR) spectroscopy as a powerful technique that is uniquely capable of addressing questions on ROS dynamics in different biological specimens and cellular compartments. Due to their critical importance in muscle functions and dysfunction, we discuss in some detail spin trapping of various ROS and focus on EPR detection of nitric oxide before highlighting how EPR can be utilized to probe biophysical characteristics of the environment surrounding a given stable radical. Despite the demonstrated ability of EPR spectroscopy to provide unique information on the identity, quantity, dynamics and environment of radical species, its applications in the field of muscle physiology, fatiguing and ageing are disproportionately infrequent. While reviewing the limited examples of successful EPR applications in muscle biology we conclude that the field would greatly benefit from more studies exploring ROS sources and kinetics by spin trapping, protein dynamics by site-directed spin labelling, and membrane dynamics and global redox changes by spin probing EPR approaches. © 2016 The Authors. The Journal of Physiology © 2016 The Physiological Society.

Physiological and pathophysiological reactive oxygen species as probed by EPR spectroscopy: the underutilized research window on muscle ageing

PubMed Central

A. Abdel‐Rahman, Engy; Mahmoud, Ali M.; Khalifa, Abdulrahman M.

2016-01-01

Abstract Reactive oxygen and nitrogen species (ROS and RNS) play crucial roles in triggering, mediating and regulating physiological and pathophysiological signal transduction pathways within the cell. Within the cell, ROS efflux is firmly controlled both spatially and temporally, making the study of ROS dynamics a challenging task. Different approaches have been developed for ROS assessment; however, many of these assays are not capable of direct identification or determination of subcellular localization of different ROS. Here we highlight electron paramagnetic resonance (EPR) spectroscopy as a powerful technique that is uniquely capable of addressing questions on ROS dynamics in different biological specimens and cellular compartments. Due to their critical importance in muscle functions and dysfunction, we discuss in some detail spin trapping of various ROS and focus on EPR detection of nitric oxide before highlighting how EPR can be utilized to probe biophysical characteristics of the environment surrounding a given stable radical. Despite the demonstrated ability of EPR spectroscopy to provide unique information on the identity, quantity, dynamics and environment of radical species, its applications in the field of muscle physiology, fatiguing and ageing are disproportionately infrequent. While reviewing the limited examples of successful EPR applications in muscle biology we conclude that the field would greatly benefit from more studies exploring ROS sources and kinetics by spin trapping, protein dynamics by site‐directed spin labelling, and membrane dynamics and global redox changes by spin probing EPR approaches. PMID:26801204

Adsorption properties of AlN on Si(111) surface: A density functional study

NASA Astrophysics Data System (ADS)

Yuan, Yinmei; Zuo, Ran; Mao, Keke; Tang, Binlong; Zhang, Zhou; Liu, Jun; Zhong, Tingting

2018-04-01

In the process of preparing GaN on Si substrate by MOCVD, an AlN buffer layer is very important. In this study, we conducted density functional theory calculations on the adsorption of AlN molecule on Si(111)-(2 × 2) surface, with the AlN molecule located horizontally or vertically above Si(111) surface at different adsorption sites. The calculations revealed that the lowest adsorption energy was at the N-top-Al-bridge site in the horizontal configuration, with the narrowest band gap, indicating that it was the most preferential adsorption growth status of AlN. In the vertical configurations, N adatom was more reactive and convenient to form bonds with the topmost Si atoms than Al adatom. When the N-end of the AlN molecule was located downward, the hollow site was the preferred adsorption site; when the Al-end was located downward, the bridge site was the most energetically favorable. Moreover, we investigated some electronic properties such as partial density of states, electron density difference, Mulliken populations, etc., revealing the microscale mechanism for AlN adsorption on Si(111) surface and providing theoretical support for adjusting the processing parameters during AlN or GaN production.

Theoretical evaluation on selective adsorption characteristics of alkali metal-based sorbents for gaseous oxidized mercury.

PubMed

Tang, Hongjian; Duan, Yufeng; Zhu, Chun; Cai, Tianyi; Li, Chunfeng; Cai, Liang

2017-10-01

Alkali metal-based sorbents are potential for oxidized mercury (Hg 2+ ) selective adsorption but show hardly effect to elemental mercury (Hg 0 ) in flue gas. Density functional theory (DFT) was employed to investigate the Hg 0 and HgCl 2 adsorption mechanism over alkali metal-based sorbents, including calcium oxide (CaO), magnesium oxide (MgO), potassium chloride (KCl) and sodium chloride (NaCl). Hg 0 was found to weakly interact with CaO (001), MgO (001), KCl (001) and NaCl (001) surfaces while HgCl 2 was effectively adsorbed on top-O and top-Cl sites. Charge transfer and bond population were calculated to discuss the covalency and ionicity of HgCl 2 bonding with the adsorption sites. The partial density of states (PDOS) analysis manifests that HgCl 2 strongly interacts with surface sites through the orbital hybridizations between Hg and top O or Cl. Frontier molecular orbital (FMO) energy and Mulliken electronegativity are introduced as the quantitative criteria to evaluate the reactivity of mercury species and alkali metal-based sorbents. HgCl 2 is identified as a Lewis acid and more reactive than Hg 0 . The Lewis basicity of the four alkali metal-based sorbents is predicted as the increasing order: NaCl < MgO < KCl < CaO, in consistence with the trend of HgCl 2 adsorption energies. Copyright © 2017 Elsevier Ltd. All rights reserved.

Design strategies of fluorescent probes for selective detection among biothiols.

PubMed

Niu, Li-Ya; Chen, Yu-Zhe; Zheng, Hai-Rong; Wu, Li-Zhu; Tung, Chen-Ho; Yang, Qing-Zheng

2015-10-07

Simple thiol derivatives, such as cysteine (Cys), homocysteine (Hcy), and glutathione (GSH), play key roles in biological processes, and the fluorescent probes to detect such thiols in vivo selectively with high sensitivity and fast response times are critical for understanding their numerous functions. However, the similar structures and reactivities of these thiols pose considerable challenges to the development of such probes. This review focuses on various strategies for the design of fluorescent probes for the selective detection of biothiols. We classify the fluorescent probes for discrimination among biothiols according to reaction types between the probes and thiols such as cyclization with aldehydes, conjugate addition-cyclization with acrylates, native chemical ligation, and aromatic substitution-rearrangement.

Experimental and theoretical study using DFT method for the competitive adsorption of two cationic dyes from wastewaters

NASA Astrophysics Data System (ADS)

Regti, Abdelmajid; Ayouchia, Hicham Ben El; Laamari, My Rachid; Stiriba, Salah Eddine; Anane, Hafid; Haddad, Mohammadine El

2016-12-01

The adsorption of cationic dyes, Basic Yellow (BY28) and Methylene Blue (MB) on a new activated carbon from medlar species were studied in both single and binary system. Some experimental parameters, namely, pH, amount of adsorbent and contact time are studied. Quantum chemical results indicate that the adsorption efficiency was directly related to the dye electrophilicity power. Some theorical parameters were calculated and proved that MB is more electrophilic than BY28, than greatest interaction with surface sites. Kinetic study showed that the adsorption follows the pseudo-second-order model and Freundlich was the best model to describe the phenomenon in the single and binary system. According to the local reactivity results using Parr functions, the sulphur and nitrogen atoms will be the main adsorption sites.

In Situ FT-IR Spectroscopic Study of CO2 and CO Adsorption on Y2O3, ZrO2, and Yttria-Stabilized ZrO2

PubMed Central

2013-01-01

In situ FT-IR spectroscopy was exploited to study the adsorption of CO2 and CO on commercially available yttria-stabilized ZrO2 (8 mol % Y, YSZ-8), Y2O3, and ZrO2. All three oxides were pretreated at high temperatures (1173 K) in air, which leads to effective dehydroxylation of pure ZrO2. Both Y2O3 and YSZ-8 show a much higher reactivity toward CO and CO2 adsorption than ZrO2 because of more facile rehydroxylation of Y-containing phases. Several different carbonate species have been observed following CO2 adsorption on Y2O3 and YSZ-8, which are much more strongly bound on the former, due to formation of higher-coordinated polydentate carbonate species upon annealing. As the crucial factor governing the formation of carbonates, the presence of reactive (basic) surface hydroxyl groups on Y-centers was identified. Therefore, chemisorption of CO2 most likely includes insertion of the CO2 molecule into a reactive surface hydroxyl group and the subsequent formation of a bicarbonate species. Formate formation following CO adsorption has been observed on all three oxides but is less pronounced on ZrO2 due to effective dehydroxylation of the surface during high-temperature treatment. The latter generally causes suppression of the surface reactivity of ZrO2 samples regarding reactions involving CO or CO2 as reaction intermediates. PMID:24009780

Evaluation of ferrolysis in arsenate adsorption on the paddy soil derived from an Oxisol.

PubMed

Jiang, Jun; Dai, Zhaoxia; Sun, Rui; Zhao, Zhenjie; Dong, Ying; Hong, Zhineng; Xu, Renkou

2017-07-01

Iron oxides are dominant effective adsorbents for arsenate in iron oxide-rich variable charge soils. Oxisol-derived paddy soils undergo intensive ferrolysis, which results in high leaching and transformation of iron oxides. However, little information is available concerning the effect of ferrolysis on arsenate adsorption by paddy soil and parent Oxisol. In the present study, we examined the arsenate affinity of soils using arsenate adsorption/desorption isotherms, zeta potential, adsorption kinetics, pH effect and phosphate competition experiments. Results showed that ferrolysis in an alternating flooding-drying Oxisol-derived paddy soil resulted in a significant decrease of free iron oxides and increase of amorphous iron oxides in the surface and subsurface layers. There were more reactive sites exposed on amorphous than on crystalline iron oxides. Therefore, disproportionate ratios of arsenate adsorption capacities and contents of free iron oxides were observed in the studied Oxisols compared with paddy soils. The Gibbs free energy values corroborated that both electrostatic and non-electrostatic adsorption mechanisms contributed to the arsenate adsorption by bulk soils, and the kinetic adsorption data further suggested that the rate-limiting step was chemisorption. The zeta potential of soil colloids decreased after arsenate was adsorbed on the surfaces, forming inner-sphere complexes and thus transferring their negative charges to the soil particle surfaces. The adsorption/desorption isotherms showed that non-electrostatic adsorption was the main mechanism responsible for arsenate binding to the Oxisol and derived paddy soils, representing 91.42-94.65% of the adsorption capacities. Further studies revealed that arsenate adsorption was greatly inhibited by increasing suspension pH and incorporation of phosphate. Copyright © 2017 Elsevier Ltd. All rights reserved.

Adsorption of thiophene on transition metal surfaces with the inclusion of van der Waals effects

NASA Astrophysics Data System (ADS)

Malone, Walter; Matos, Jeronimo; Kara, Abdelkader

2018-03-01

We use density functional theory with the inclusion of the van der Waals interaction to study the adsorption of thiophene, C4H4S, on Pt, Rh, Pd, Au, and Ag (100) surfaces. The five van der Waals (vdW) inclusive functionals we employ are optB86b-vdW, optB88-vdW, optPBE-vdW, revPBE-vdW, and rPW86-vdW2. For comparison we also run calculations with the GGA- Perdew Burke and Ernzerhof (PBE) functional. We examine several adsorption sites with the plane of the molecule parallel or perpendicular to the surface. The most stable configuration on all metals was the site where the center of the thiophene lies over a 4-fold hollow site with the sulfur atom lying close to a top site. Furthermore, we examine several electronic and geometric properties of the adsorbate including charge transfer, modification of the d-band, adsorption energy, tilt angle, and adsorption height. For the coinage metals PBE gives the lowest adsorption energy. For reactive transition metal substrates, revPBE-vdW and rPW86-vdW2 give lower adsorption energies than PBE.

Sandwich hybridization probes for the detection of Pseudo-nitzschia (Bacillariophyceae) species: An update to existing probes and a description of new probes.

PubMed

Bowers, Holly A; Marin, Roman; Birch, James M; Scholin, Christopher A

2017-12-01

New sandwich hybridization assay (SHA) probes for detecting Pseudo-nitzschia species (P. arenysensis, P. fraudulenta, P. hasleana, P. pungens) are presented, along with updated cross-reactivity information on historical probes (SHA and FISH; fluorescence in situ hybridization) targeting P. australis and P. multiseries. Pseudo-nitzschia species are a cosmopolitan group of diatoms that produce varying levels of domoic acid (DA), a neurotoxin that can accumulate in finfish and shellfish and transfer throughout the food web. Consumption of infected food sources can lead to illness in humans (amnesic shellfish poisoning; ASP) and marine wildlife (domoic acid poisoning; DAP). The threat of human illness, along with economic loss from fishery closures has resulted in the implementation of monitoring protocols and intensive ecological studies. SHA probes have been instrumental in some of these efforts, as the technique performs well in complex heterogeneous sample matrices and has been adapted to benchtop and deployable (Environmental Sample Processor) platforms. The expanded probe set will enhance future efforts towards understanding spatial, temporal and successional patterns in species during bloom and non-bloom periods. Copyright © 2017 Elsevier B.V. All rights reserved.

Zinc (hydr)oxide/graphite oxide/AuNPs composites: role of surface features in H₂S reactive adsorption.

PubMed

Giannakoudakis, Dimitrios A; Bandosz, Teresa J

2014-12-15

Zinc hydroxide/graphite oxide/AuNPs composites with various levels of complexity were synthesized using an in situ precipitation method. Then they were used as H2S adsorbents in visible light. The materials' surfaces were characterized before and after H2S adsorption by various physical and chemical methods (XRD, FTIR, thermal analysis, potentiometric titration, adsorption of nitrogen and SEM/EDX). Significant differences in surface features and synergistic effects were found depending on the materials' composition. Addition of graphite oxide and the deposition of gold nanoparticles resulted in a marked increase in the adsorption capacity in comparison with that on the zinc hydroxide and zinc hydroxide/AuNP. Addition of AuNPs to zinc hydroxide led to a crystalline ZnO/AuNP composite while the zinc hydroxide/graphite oxide/AuNP composite was amorphous. The ZnOH/GO/AuNPs composite exhibited the greatest H2S adsorption capacity due to the increased number of OH terminal groups and the conductive properties of GO that facilitated the electron transfer and consequently the formation of superoxide ions promoting oxidation of hydrogen sulfide. AuNPs present in the composite increased the conductivity, helped with electron transfer to oxygen, and prevented the fast recombination of the electrons and holes. Copyright © 2014 Elsevier Inc. All rights reserved.

Probing nanodispersions of clays for reactive foaming.

PubMed

Harikrishnan, G; Lindsay, Chris I; Arunagirinathan, M A; Macosko, Christopher W

2009-09-01

Nanodispersions of clays in polyurethane components have been prepared. Nanoclays (both natural and organically modified) of various aspect ratios are used. The fillers are dispersed separately in polyurethane components, viz., polyol and polyisocyanate. The nanodispersions are characterized by the combined use of solution rheology, X-ray scattering, cryo-electron microscopy, and IR spectroscopy. Reactive foaming of these nanodispersions is carried out to make polyurethane nanocomposite foams. The status of the dispersion of fillers in components and in foams has been compared to investigate the effect of the foaming process in exfoliation. Interpretation of the results from different characterization techniques describes the state of the dispersion of fillers in components and in foam. The rheological and physicochemical behaviors of nanodispersions are shown to have a significant influence on the properties of nanocomposite foams.

Probing adsorption sites of carbon dioxide in metal organic framework of [Zn(bdc)(dpds)]n: A molecular simulation study

NASA Astrophysics Data System (ADS)

Lu, Shih-I.; Liao, Jian-Min; Huang, Xiao-Zhuang; Lin, Chia-Hsun; Ke, Szu-Yu; Wang, Chih-Chieh

2017-11-01

We used force-field based grand-canonical Monte Carlo simulation method and density functional theory to study adsorption characteristics of carbon dioxide (CO2) molecules in a metal-organic framework (MOF) compound, [Zn(bdc)(dpds)]n. The studied MOF include a metal ion (Zn(II)), an anion organic linker (dianion of benzene dicarboxylicacid, bdc2-) and a neutral organic linker (4,4‧-dipyridyldisulfide, dpds). Results from calculated adsorption isotherms and enthalpies of adsorption agree with the experimental data. The interactions between the adsorbed CO2 and the organic linkers were examined in simulations. Calculated results show available absorption sites are surrounded by two dpds ligands in which an S-S bond as an N-N‧ spacer connect two pyridines. In contrast, the bdc2- ligand does not give a significant contribution to the substantial adsorption amount even though it contains the carboxylate group that provides available bonding site to CO2.

Fabrication of Cantilever-Bump Type Si Probe Card

NASA Astrophysics Data System (ADS)

Park, Jeong-Yong; Lee, Dong-Seok; Kim, Dong-Kwon; Lee, Jong-Hyun

2000-12-01

Probe card is most important part in the test system which selects the good or bad chip of integrated circuit (IC) chips. Silicon vertical probe card is able to test multiple semiconductor chips simultaneously. We presented cantilever-bump type vertical probe card. It was fabricated by dry etching using RIE(reactive ion etching) technique and porous silicon micromachining using silicon direct bonded (SDB) wafer. Cantilevers and bumps were fabricated by isotropic etching using RIE@. 3-dimensional structures were formed by porous silicon micromachining technique using SDB wafer. Contact resistance of fabricated probe card was less than 2 Ω and its life time was more than 200,000 turns. The process used in this work is very simple and reproducible, which has good controllability in the tip dimension and spacing. It is expected that the fabricated probe card can reduce testing time, can promote productivity and enables burn-in test.

Subclass-specific labeling of protein-reactive natural products with customized nucleophilic probes.

PubMed

Rudolf, Georg C; Koch, Maximilian F; Mandl, Franziska A M; Sieber, Stephan A

2015-02-23

Natural products represent a rich source of bioactive compounds that constitute a large fraction of approved drugs. Among those are molecules with electrophilic scaffolds, such as Michael acceptors, β-lactams, and epoxides that irreversibly inhibit essential enzymes based on their catalytic mechanism. In the search for novel bioactive molecules, current methods are challenged by the frequent rediscovery of known chemical entities. Herein small nucleophilic probes that attack electrophilic natural products and enhance their detection by HPLC-UV and HPLC-MS are introduced. A screen of diverse probe designs revealed one compound with a desired selectivity for epoxide- and maleimide-based antibiotics. Correspondingly, the natural products showdomycin and phosphomycin could be selectively targeted in extracts of their natural producing organism, in which the probe-modified molecules exhibited superior retention and MS detection relative to their unmodified counterparts. This method may thus help to discover small, electrophilic molecules that might otherwise easily elude detection in complex samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The adsorption and thermal decomposition of PH 3 on Si(111)-(7 × 7)

NASA Astrophysics Data System (ADS)

Taylor, P. A.; Wallace, R. M.; Choyke, W. J.; Yates, J. T.

1990-11-01

The adsorption of PH 3, on Si(111)-(7 × 7) has been studied by Auger electron spectroscopy and temperature programmed desorption. PH 3 was found to exhibit two kinds of behavior on the surface. A small surface coverage of molecularly adsorbed PH 3 desorbs without any dissociative surface chemistry. For the majority of the adsorbed PH x species (3 ⩾ x ⩾ 1) dissociation occurs to form P(a) and H(a). At 120 K, PH 3 initially adsorbs as the reactive species with a sticking coefficient of S ≅ 1 up to ˜75% saturation. The reactive PH x species surface concentration saturates at (1.9 ± 0.3) × 10 14 PH x cm -2. Surface H(a), produc thermal decomposition, desorbs as H 2(g) at T > 700 K., and P(a) desorbs as P 2(g) at T > 900 K. Capping the Si-dangling bonds with atomic deuterium prevents PH 3 adsorption, indicating that the dangling bonds are the PH 3 adsorption sites. Isotopic studies involving Si-D surface species mixed with adsorbed PH x species indicate that PH 3 desorption does not occur through a recombination process. Finally, additional PH 3 may be adsorbed if the surface hydrogen produced by dissociation of PH 3 is removed. Evidence for P penetration into bulk Si(111) at 875 K is presented.

Water vapor adsorption on goethite.

PubMed

Song, Xiaowei; Boily, Jean-François

2013-07-02

Goethite (α-FeOOH) is an important mineral contributing to processes of atmospheric and terrestrial importance. Their interactions with water vapor are particularly relevant in these contexts. In this work, molecular details of water vapor (0.0-19.0 Torr; 0-96% relative humidity at 25 °C) adsorption at surfaces of synthetic goethite nanoparticles reacted with and without HCl and NaCl were resolved using vibrational spectroscopy. This technique probed interactions between surface (hydr)oxo groups and liquid water-like films. Molecular dynamics showed that structures and orientations adopted by these waters are comparable to those adopted at the interface with liquid water. Particle surfaces reacted with HCl accumulated less water than acid-free surfaces due to disruptions in hydrogen bond networks by chemisorbed waters and chloride. Particles reacted with NaCl had lower loadings below ∼10 Torr water vapor but greater loadings above this value than salt-free surfaces. Water adsorption reactions were here affected by competitive hydration of coexisting salt-free surface regions, adsorbed chloride and sodium, as well as precipitated NaCl. Collectively, the findings presented in this study add further insight into the initial mechanisms of thin water film formation at goethite surfaces subjected to variations in water vapor pressure that are relevant to natural systems.

Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar

PubMed Central

Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin

2018-01-01

This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)2 saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER. PMID:29621188

Chloride Ion Adsorption Capacity of Anion Exchange Resin in Cement Mortar.

PubMed

Lee, Yunsu; Lee, Hanseung; Jung, Dohyun; Chen, Zhengxin; Lim, Seungmin

2018-04-05

This paper presents the effect of anion exchange resin (AER) on the adsorption of chloride ions in cement mortar. The kinetic and equilibrium behaviors of AER were investigated in distilled water and Ca(OH)₂ saturated solutions, and then the adsorption of chloride ions by the AER in the mortar specimen was determined. The AER was used as a partial replacement for sand in the mortar specimen. The mortar specimen was coated with epoxy, except for an exposed surface, and then immersed in a NaCl solution for 140 days. The chloride content in the mortar specimen was characterized by energy dispersive X-ray fluorescence analysis and electron probe microanalysis. The results showed that the AER could adsorb the chloride ions from the solution rapidly but had a relatively low performance when the pH of its surrounding environment increased. When the AER was mixed in the cement mortar, its chloride content was higher than that of the cement matrix around it, which confirms the chloride ion adsorption capacity of the AER.

Liquid-phase separation of reactive dye by wood-rotting fungus: a biotechnological approach.

PubMed

Binupriya, Arthur R; Sathishkumar, Muthuswamy; Dhamodaran, Kavitha; Jayabalan, Rasu; Swaminathan, Krishnaswamy; Yun, Sei Eok

2007-08-01

The live and pretreated mycelial pellets/biomass of Trametes versicolor was used for the biosorption of a textile dye, reactive blue MR (RBMR) from aqueous solution. The parameters that affect the biosorption of RBMR, such as contact time, concentration of dye and pH, on the extent of RBMR adsorption were investigated. To develop an effective and accurate design model for removal of dye, adsorption kinetics and equilibrium data are essential basic requirements. Lagergren first-order, second-order and Bangham's model were used to fit the experimental data. Results of the kinetic studies showed that the second order kinetic model fitted well for the present experimental data. The Langmuir, Freundlich and Temkin adsorption models were used for the mathematical description of the biosorption equilibrium. The biosorption equilibrium data obeyed well for Langmuir isotherm and the maximum adsorption capacities were found to be 49.8, 51.6, 47.4 and 46.7 mg/g for live, autoclaved, acid- and alkali-pretreated biomass. The dye uptake capacity order of the fungal biomass was found as autoclaved > live > acid-treated > alkali-pretreated. The Freundlich and Temkin models were also able to describe the biosorption equilibrium on RBMR on live and pretreated fungal biomass. Acidic pH was favorable for the adsorption of dye. Studies on pH effect and desorption show that chemisorption seems to play a major role in the adsorption process. On comparison with fixed bed adsorption, batch mode adsorption was more efficient in adsorption of RBMR.

Antigenic cross-reactivity between Schistosoma mansoni and peanut: a role for cross-reactive carbohydrate determinants (CCDs) and implications for the hygiene hypothesis.

PubMed

Igetei, Joseph E; El-Faham, Marwa; Liddell, Susan; Doenhoff, Michael J

2017-04-01

The antigenic reactivity of constituents of Schistosoma mansoni and peanut (Arachis hypogaea) was investigated to determine whether identical antigenic epitopes possessed by both organisms provided a possible explanation for the negative correlation between chronic schistosome infection and atopy to allergens. Aqueous extracts of peanuts were probed in Western immunoblots with rabbit IgG antibodies raised against the egg, cercarial and adult worm stages of S. mansoni. Several molecules in the peanut extract were antigenically reactive with antibodies from the various rabbit anti-schistosome sera. A pair of cross-reactive peanut molecules at ~30 000-33 000 molecular weight was purified and both proteins were identified by mass spectrometric analysis as the peanut allergen Ara h 1. Anti-S. mansoni soluble egg antigen antibodies that were eluted off the peanut molecules reacted with two S. mansoni egg antigens identified by mass spectrometry as IPSE/α-1 and κ-5. Alignments of the amino acid sequences of Ara h 1 and either IPSE/α-1 or κ-5 revealed a low level of peptide sequence identity. Incubation of nitrocellulose paper carrying electrophoresed peanut molecules, six constituents of other allergic plants and S. mansoni egg antigens in a mild solution of sodium metaperiodate before probing with antibodies, inhibited most of the cross-reactivities. The results are consistent with the antigenic cross-reactive epitopes of S. mansoni egg antigens, peanut and other allergic plants being cross-reactive carbohydrate determinants (CCDs). These findings are novel and an explanation based on 'blocking antibodies' could provide an insight for the inverse relationship observed between schistosome infection and allergies. © 2017 John Wiley & Sons Ltd.

Adsorption of poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) polymers on zinc, zinc oxide, iron, and iron oxide surfaces.

PubMed

Seifert, Susan; Simon, Frank; Baumann, Giesela; Hietschold, Michael; Seifert, Andreas; Spange, Stefan

2011-12-06

The adsorption of poly(vinyl formamide) (PVFA) and the statistic copolymers poly(vinyl formamide-co-vinyl amine) (PVFA-co-PVAm) onto zinc and iron metal particles as well as their oxides was investigated. The adsorbates were characterized by means of XPS, DRIFT spectroscopy, wet chemical analysis, and solvatochromic probes. Dicyano-bis-(1,10-phenanthroline)-iron(II) (1), 3-(4-amino-3-methylphenyl)-7-phenyl-benzo-[1,2-b:4,5-b']difuran-2,6-dione (2), and 4-tert-butyl-2-(dicyano-methylene)-5-[4-(diethylamino)-benzylidene]-Δ(3)-thiazoline (3) as solvatochromic probes were coadsorbed onto zinc oxide to measure various effects of surface polarity. The experimental findings showed that the adsorption mechanism of PVFA and PVFA-co-PVAm strongly depends on the degree of hydrolysis of PVFA and pH values and also on the kind of metal or metal oxide surfaces that were employed as adsorbents. The adsorption mechanism of PVFA/PVFA-co-PVAm onto zinc oxide and iron oxide surfaces is mainly affected by electrostatic interactions. Particularly in the region of pH 5, the adsorption of PVFA/PVFA-co-PVAm onto zinc and iron metal particles is additionally influenced by redox processes, dissolution, and complexation reactions. © 2011 American Chemical Society

Ab initio study of aspirin adsorption on single-walled carbon and carbon nitride nanotubes

NASA Astrophysics Data System (ADS)

Lee, Yongju; Kwon, Dae-Gyeon; Kim, Gunn; Kwon, Young-Kyun

We use ab intio density functional theory to investigate the adsorption properties of acetylsalicylic acid or aspirin on a (10, 0) carbon nanotube (CNT) and a (8, 0) triazine-based graphitic carbon nitride nanotube (CNNT). It is found that an aspirin molecule binds stronger to the CNNT with its adsorption energy of 0.67 eV than to the CNT with 0.51 eV. The stronger adsorption energy on the CNNT is ascribed to the high reactivity of its N atoms with high electron affinity. The CNNT exhibits local electric dipole moments, which cause strong charge redistribution in the aspirin molecule adsorbed on the CNNT than on the CNT. We also explore the influence of an external electric field on the adsorption properties of aspirin on these nanotubes by examining the modifications in their electronic band structures, partial densities of states, and charge distributions. It is found that an electric field applied along a particular direction induces aspirin molecular states in the in-gap region of the CNNT implying a potential application of aspirin detection.

CdS/TiO2-fluorescein isothiocyanate nanoparticles as fluorescence resonance energy transfer probe for the determination of trace alkaline phosphatase based on affinity adsorption assay.

PubMed

Liu, Jia-Ming; Lin, Li-ping; Jiao, Li; Cui, Ma-Lin; Wang, Xin-Xing; Zhang, Li-Hong; Zheng, Zhi-Yong

2012-08-30

The CdS/TiO(2)-fluorescein isothiocyanate (FITC) luminescent nanoparticles (CdS/TiO(2)-FITC) with the particle size of 20 nm have been synthesized by sol-gel method. CdS/TiO(2)-FITC could emit the fluorescence of both FITC and CdS/TiO(2). The fluorescence resonance energy transfer (FRET) occurred between the donor CdS/TiO(2) and the acceptor FITC in the CdS/TiO(2)-FITC. Taking advantages of the excellent characteristics of FRET, a new CdS/TiO(2)-FITC FRET labeling reagent and a CdS/TiO(2)-FITC-wheat germ agglutinin (CdS/TiO(2)-FITC-WGA) fluorescent probe have been developed. The FRET occurring between the donor CdS/TiO(2) and the acceptor FITC in the labelled product CdS/TiO(2)-FITC-WGA-AP, formed in the affinity adsorption reaction between the WGA in this CdS/TiO(2)-FITC-WGA fluorescent probe and alkaline phosphatase (AP), sharply enhanced the fluorescence signal of FITC and quench the fluorescence signal of CdS/TiO(2). Moreover, the ΔF (the change of the fluorescence signal) of FITC and CdS/TiO(2) were proportional to the content of AP, respectively. Thus, a new method that CdS/TiO(2)-fluorescein isothiocyanate nanoparticles for the determination of trace AP based on FRET-affinity adsorption assay has been established. The limit of quantification (LOQ) of the method was 1.3×10(-17) g AP mL(-1) for CdS/TiO(2) and 1.1×10(-17) g AP mL(-1) for FITC, respectively. This sensitive, rapid, high selective and precise method has been applied to the determination of AP in human serum and the prediction of human disease with the results agreed well with enzyme-linked immunosorbent assay (ELISA) in Zhangzhou Municipal Hospital of Fujian Province. Simultaneously, the reaction mechanism for the determination of AP was also discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Pore size dependent molecular adsorption of cationic dye in biomass derived hierarchically porous carbon.

PubMed

Chen, Long; Ji, Tuo; Mu, Liwen; Shi, Yijun; Wang, Huaiyuan; Zhu, Jiahua

2017-07-01

Hierarchically porous carbon adsorbents were successfully fabricated from different biomass resources (softwood, hardwood, bamboo and cotton) by a facile two-step process, i.e. carbonization in nitrogen and thermal oxidation in air. Without involving any toxic/corrosive chemicals, large surface area of up to 890 m 2 /g was achieved, which is comparable to commercial activated carbon. The porous carbons with various surface area and pore size were used as adsorbents to investigate the pore size dependent adsorption phenomenon. Based on the density functional theory, effective (E-SSA) and ineffective surface area (InE-SSA) was calculated considering the geometry of used probing adsorbate. It was demonstrated that the adsorption capacity strongly depends on E-SSA instead of total surface area. Moreover, a regression model was developed to quantify the adsorption capacities contributed from E-SSA and InE-SSA, respectively. The applicability of this model has been verified by satisfactory prediction results on porous carbons prepared in this work as well as commercial activated carbon. Revealing the pore size dependent adsorption behavior in these biomass derived porous carbon adsorbents will help to design more effective materials (either from biomass or other carbon resources) targeting to specific adsorption applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structural and adsorptive properties of activated carbons prepared by carbonization and activation of resins.

PubMed

Leboda, R; Skubiszewska-Zieba, J; Tomaszewski, W; Gun'ko, V M

2003-07-15

Four activated carbons (S1-S4) possessing different structural characteristics were prepared by carbonization of commercial resins (used for ion exchange) and subsequent activation. Their textural parameters were determined on the basis of nitrogen adsorption-desorption at 77.4 K, analyzed by applying several local and overall adsorption isotherm equations. The nature of carbon surface functionalities was analyzed by FTIR spectroscopy. The GC and solid-phase extraction (SPE) techniques were applied to study the influence of the texture of carbonaceous materials on their adsorptive properties. The adsorption efficiency of synthesized carbons with respect to alkylhalides used as probe compounds in the GC measurements varied over a range from 28% (C(2)H(3)Cl(3)/S2) to 85% (CHBr(3)/S1) depending on the type of adsorbates and adsorbents. The concentrating efficiency of these carbons in SPE of explosive materials changed over a larger range from 12% (trinitroglycerin/S4) and 13% (trinitrotoluene/S2) up to 100% (octogen/S1). Active carbon prepared using Zerolite 225x8 as a precursor demonstrated better results than other carbons in two types of adsorption with average values of the efficiency of 75.4% for explosives and 60.8% for alkylhalides.

Efficient adsorption and photocatalytic degradation of organic pollutants diluted in water using fluoride-modified hydrophobic mesoporous silica

NASA Astrophysics Data System (ADS)

Yamashita, Hiromi; Maekawa, Kazuhiro; Nakao, Hidetoshi; Anpo, Masakazu

2004-10-01

Using a mixture of tetraethylammonium fluoride and dodecylamine as templates, hydrophobic mesoporous silica supports were prepared. The fine anatase TiO 2 photocatalysts were prepared on the fluoride-modified hydrophobic mesoporous silica and the adsorption properties and the photocatalytic degradation of an aqueous 2-propanol or 2-hexanol solution into CO 2 and H 2O have been studied. The amount of adsorption and the photocatalytic reactivities increased with increasing the content of fluoride ions on these photocatalysts. 2-Hexanol diluted in water was adsorbed on the hydrophobic catalysts more efficiently than 2-propanol.

Dimethyl methylphosphonate adsorption and decomposition on MoO2 as studied by ambient pressure x-ray photoelectron spectroscopy and DFT calculations

NASA Astrophysics Data System (ADS)

Head, Ashley R.; Tsyshevsky, Roman; Trotochaud, Lena; Yu, Yi; Karslıoǧlu, Osman; Eichhorn, Bryan; Kuklja, Maija M.; Bluhm, Hendrik

2018-04-01

Organophosphonates range in their toxicity and are used as pesticides, herbicides, and chemical warfare agents (CWAs). Few laboratories are equipped to handle the most toxic molecules, thus simulants such as dimethyl methylphosphonate (DMMP), are used as a first step in studying adsorption and reactivity on materials. Benchmarked by combined experimental and theoretical studies of simulants, calculations offer an opportunity to understand how molecular interactions with a surface changes upon using a CWA. However, most calculations of DMMP and CWAs on surfaces are limited to adsorption studies on clusters of atoms, which may differ markedly from the behavior on bulk solid-state materials with extended surfaces. We have benchmarked our solid-state periodic calculations of DMMP adsorption and reactivity on MoO2 with ambient pressure x-ray photoelectron spectroscopy studies (APXPS). DMMP is found to interact strongly with a MoO2 film, a model system for the MoO x component in the ASZM-TEDA© gas filtration material. Density functional theory modeling of several adsorption and decomposition mechanisms assist the assignment of APXPS peaks. Our results show that some of the adsorbed DMMP decomposes, with all the products remaining on the surface. The rigorous calculations benchmarked with experiments pave a path to reliable and predictive theoretical studies of CWA interactions with surfaces.

Effect of Doping on Surface Reactivity and Conduction Mechanism in Sm-doped CeO2 Thin Films

DOE PAGES

Yang, Nan; Belianinov, Alex; Strelcov, Evgheni; ...

2014-11-21

Scanning probe microscopy measurements show irreversible surface electrochemistry in Sm-doped CeO2 thin films, which depends on humidity, temperature and doping concentration. A systematic study by electrochemical strain microscopy (ESM) in samples with two different Sm content and in several working conditions allows disclosing the microscopic mechanism underlying the difference in water adsorption and splitting with subsequent proton liberation. We measure the behavior of the hysteresis loops by changing temperature and humidity, both in standard ESM configuration and using the first order reversal curve (FORC) method. Complementing our study with spectroscopic measurements by hard x-ray photoemission spectroscopy we find that watermore » incorporation is favored until the doping with Sm is too high to allow the presence of Ce3+. The influence of doping on the surface reactivity and conduction mechanism clearly emerges from all of our experimental results. We find that at lower Sm concentration proton conduction is prevalent, featured by lower activation energy and higher mobility. Defect concentrations determine the type of the prevalent charge carrier in a doping dependent manner.« less

Diels-Alder and Stille Coupling Approach for the Short Protecting-Group-Free Synthesis of Mycophenolic Acid, Its Phenylsulfenyl and Phenylselenyl Analogues, and Reactive Oxygen Species (ROS) Probing Capacity in Water.

PubMed

Halle, Mahesh B; Yudhistira, Tesla; Lee, Woo-Hyun; Mulay, Sandip V; Churchill, David G

2018-06-15

A short, protecting-group-free synthesis is achieved. The synthesis is step-efficient and general. A Diels-Alder and Stille cross-coupling approach includes key transformations, allowing for a competitive synthesis which involves a rare halophenol Stille cross-coupling study. The phenylselenyl and phenylsulfenyl analogues were prepared as novel compounds in good overall yield. The applicability of one of the intermediates as a potential probe for reactive oxygen species (ROS) in water is investigated.

Adsorption properties of chloropicrin on pristine and borazine-doped nanographenes: A theoretical study

NASA Astrophysics Data System (ADS)

Hosseinian, Akram; Vessally, Esmail; Babazadeh, Mirzaagha; Edjlali, Ladan; Es'haghi, Moosa

2018-04-01

Recently, nanographenes were introduced as definite segments of graphene where their end atoms are saturated with hydrogens. In this study, we explored the reactivity and electronic sensitivity of a hexa-peri-hexabenzocoronene (HBC) and newly synthesized borazine-like ring-doped nanographenes (BNG) to the chloropicrin molecule based on density functional theory. We found that chloropicrin is preferentially adsorbed via its N atoms on both HBC and BNG nanographenes. The electronic properties of HBC were predicted to be sensitive to chloropicrin but the adsorption capacity is low because of the small adsorption energy (-7.1 kcal/mol). However, chloropicrin is adsorbed somewhat more strongly on BNG, with an adsorption energy of about -29.9 kcal/mol. After the adsorption of chloropicrin, the lowest unoccupied molecular orbital (LUMO) level of BNG stabilizes and the highest occupied molecular orbital-LUMO gap is decreased by about 85.9%. Thus, BNG converts from a semiconductor into a semimetal with a higher electrical conductivity. The change in electrical conductivity can generate an electrical signal, which is helpful for detecting chloropicrin. In addition, we predicted a short recovery time of 14.6 s at 350 K for this sensor.

Reactivity improvement of Ca(OH)2 sorbent using diatomaceous earth (DE) from Aceh Province

NASA Astrophysics Data System (ADS)

Mariana, M.; Mahidin, M.; Mulana, F.; Agam, T.; Hafdiansyah, F.

2018-04-01

In this study, the diatomaceous earth (DE) from Aceh Province was used to increase the reactivity of Ca(OH)2sorbent. The high silica (SiO2) content of about 97% in the diatomaceous earth allows the increasing reactivity of Ca(OH)2sorbent by forming calcium silicate hydrate (CSH). The CSH improved the porosity characteristic of the sorbent. The improvement process was performed by mixing Ca(OH)2sorbent, diatomaceous earth and water in a beaker glass at the Ca(OH)2/DE weight ratio of 1:10 for 2 hand then dried at 120 °C for 24 h. The dried sorbent was calcined at 500 °C and 800 °C for 2 h. The activated sorbent was characterized using Scanning Electron Microscopy (SEM) for the morphological properties; X- Ray Diffraction (XRD) for the materials characteristics. The adsorption capacity of thesorbent was tested by methylene blue adsorption. The results showed that the Ca(OH)2/DEsorbent had a higher porosity than the Ca(OH)2 adsorbent.The results also showed that Ca(OH)2/DE which was calcined at higher temperature of 800 °C had a higher adsorption capacity compared to Ca(OH)2/DE which was calcined at lower temperature of 500 °C.

Activity-based probes for the ubiquitin conjugation-deconjugation machinery: new chemistries, new tools, and new insights.

PubMed

Hewings, David S; Flygare, John A; Bogyo, Matthew; Wertz, Ingrid E

2017-05-01

The reversible post-translational modification of proteins by ubiquitin and ubiquitin-like proteins regulates almost all cellular processes, by affecting protein degradation, localization, and complex formation. Deubiquitinases (DUBs) are proteases that remove ubiquitin modifications or cleave ubiquitin chains. Most DUBs are cysteine proteases, which makes them well suited for study by activity-based probes. These DUB probes report on deubiquitinase activity by reacting covalently with the active site in an enzyme-catalyzed manner. They have proven to be important tools to study DUB selectivity and proteolytic activity in different settings, to identify novel DUBs, and to characterize deubiquitinase inhibitors. Inspired by the efficacy of activity-based probes for DUBs, several groups have recently reported probes for the ubiquitin conjugation machinery (E1, E2, and E3 enzymes). Many of these enzymes, while not proteases, also posses active site cysteine residues and can be targeted by covalent probes. In this review, we will discuss how features of the probe (cysteine-reactive group, recognition element, and reporter tag) affect reactivity and suitability for certain experimental applications. We will also review the diverse applications of the current probes, and discuss the need for new probe types to study emerging aspects of ubiquitin biology. © 2017 Federation of European Biochemical Societies.

Microcalorimetric and potentiometric titration studies on the adsorption of copper by extracellular polymeric substances (EPS), minerals and their composites.

PubMed

Fang, Linchuan; Huang, Qiaoyun; Wei, Xing; Liang, Wei; Rong, Xinming; Chen, Wenli; Cai, Peng

2010-08-01

Equilibrium adsorption experiments, isothermal titration calorimetry and potentiometric titration techniques were employed to investigate the adsorption of Cu(II) by extracellular polymeric substances (EPS) extracted from Pseudomonas putida X4, minerals (montmorillonite and goethite) and their composites. Compared with predicted values of Cu(II) adsorption on composites, the measured values of Cu(II) on EPS-montmorillonite composite increased, however, those on EPS-goethite composite decreased. Potentiometric titration results also showed that more surface sites were observed on EPS-montmorillonite composite and less reactive sites were found on EPS-goethite composite. The adsorption of Cu(II) on EPS molecules and their composites with minerals was an endothermic reaction, while that on minerals was exothermic. The positive values of enthalpy change (Delta H) and entropy change (DeltaS) for Cu(II) adsorption on EPS and mineral-EPS composites indicated that Cu(II) mainly interacts with carboxyl and phosphoryl groups as inner-sphere complexes on EPS molecules and their composites with minerals. (c) 2010 Elsevier Ltd. All rights reserved.

Adsorption of hydrogen gas and redox processes in clays.

PubMed

Didier, Mathilde; Leone, Laura; Greneche, Jean-Marc; Giffaut, Eric; Charlet, Laurent

2012-03-20

In order to assess the adsorption properties of hydrogen gas and reactivity of adsorbed hydrogen, we measured H(2)(g) adsorption on Na synthetic montmorillonite-type clays and Callovo-Oxfordian (COx) clayrock using gas chromatography. Synthetic montmorillonites with increasing structural Fe(III) substitution (0 wt %, 3.2 wt %, and 6.4 wt % Fe) were used. Fe in the synthetic montmorillonites is principally present as structural Fe(III) ions. We studied the concomitant reduction of structural Fe(III) in the clays using (57)Fe Mössbauer spectrometry. The COx, which mainly contains smectite/illite and calcite minerals, is also studied together with the pure clay fraction of this clayrock. Experiments were performed with dry clay samples which were reacted with hydrogen gas at 90 and 120 °C for 30 to 45 days at a hydrogen partial pressure close to 0.45 bar. Results indicate that up to 0.11 wt % of hydrogen is adsorbed on the clays at 90 °C under 0.45 bar of relative pressure. (57)Fe Mössbauer spectrometry shows that up to 6% of the total structural Fe(III) initially present in these synthetic clays is reduced upon adsorption of hydrogen gas. No reduction is observed with the COx sample in the present experimental conditions.

Kelvin probe force microscopy studies of the charge effects upon adsorption of carbon nanotubes and C60 fullerenes on hydrogen-terminated diamond

NASA Astrophysics Data System (ADS)

Kölsch, S.; Fritz, F.; Fenner, M. A.; Kurch, S.; Wöhrl, N.; Mayne, A. J.; Dujardin, G.; Meyer, C.

2018-01-01

Hydrogen-terminated diamond is known for its unusually high surface conductivity that is ascribed to its negative electron affinity. In the presence of acceptor molecules, electrons are expected to transfer from the surface to the acceptor, resulting in p-type surface conductivity. Here, we present Kelvin probe force microscopy (KPFM) measurements on carbon nanotubes and C60 adsorbed onto a hydrogen-terminated diamond(001) surface. A clear reduction in the Kelvin signal is observed at the position of the carbon nanotubes and C60 molecules as compared with the bare, air-exposed surface. This result can be explained by the high positive electron affinity of carbon nanotubes and C60, resulting in electron transfer from the surface to the adsorbates. When an oxygen-terminated diamond(001) is used instead, no reduction in the Kelvin signal is obtained. While the presence of a charged adsorbate or a difference in work function could induce a change in the KPFM signal, a charge transfer effect of the hydrogen-terminated diamond surface, by the adsorption of the carbon nanotubes and the C60 fullerenes, is consistent with previous theoretical studies.

Surface reactivity of mercury on the oxygen-terminated hematite(0001) surface: a first-principle study

NASA Astrophysics Data System (ADS)

Jung, J. E.; Wilcox, J.

2016-12-01

Hematite (α-Fe2O3) is a common mineral found in Earth's near-surface environment. Due to its nontoxicity, corrosion-resistance, and high thermal stability, α-Fe2O3 has attracted attentions as materials for various applications such as photocatalysts, gas sensors, as well as for the removal of heavy metals. In this study, α-Fe2O3 is chosen for potential mercury (Hg) sorbent in order to remove Hg from coal-fired power plants. Specifically, theoretical approaches using density functional theory (DFT) is used to understand surface reactivity of Hg on oxygen (O) terminated α-Fe2O3(0001) surface. The most probable adsorption sites of Hg, chlorine (Cl), and mercury chloride (HgCl) on the α-Fe2O3 surface are found based on adsorption energy calculations, and the oxidation states of the adsorbates are determined by Bader charge analysis. Additionally, projected density of states (PDOS) analysis characterizes the surface-adsorbate bonding mechanism. The results of adsorption energy calculation proposes that Hg physisorbs to the α-Fe2O3(0001) surface with adsorption energy of -0.278 eV, and the subsequent Bader charge analysis confirms that Hg is slightly oxidized. In addition, Cl introduced to the Hg-adsorbed surface strengthens Hg stability on the α-Fe2O3(0001) surface as evidenced by a shortened Hg-surface equilibrium distance. The PDOS analysis also suggests that Cl enhances the chemical bonding between the surface and the adsorbate, thereby increasing adsorption strength. In summary, α-Fe2O3 has ability to adsorb and oxidize Hg, and this reactivity is enhanced in the presence of Cl.

Quantum chemical study of arsenic (III, V) adsorption on Mn-oxides: implications for arsenic(III) oxidation.

PubMed

Zhu, Mengqiang; Paul, Kristian W; Kubicki, James D; Sparks, Donald L

2009-09-01

Density functional theory (DFT) calculations were used to investigate As(V) and As(III) surface complex structures and reaction energies on both Mn(III) and Mn(IV) sites in an attempt to better understand As(III) oxidation bybirnessite, a layered Mn-dioxide mineral. Edge-sharing dioctahedral Mn(III) and Mn(IV) clusters with different combinations of surface functional groups (>MnOH and >MnOH2) were employed to mimic pH variability. Results show that As(V) adsorption was more thermodynamically favorable than As(III) adsorption on both Mn(III) and Mn(IV) surface sites under simulated acidic pH conditions. Therefore, we propose that As(V) adsorption inhibits As(III) oxidation by blocking adsorption sites. Under simulated acidic pH conditions, Mn(IV) sites exhibited stronger adsorption affinity than Mn(III) sites for both As(III) and As(V). Overall, we hypothesize that Mn(III) sites are less reactive in terms of As(III) oxidation due to their lower affinity for As(III) adsorption, higher potential to be blocked by As(V) complexes, and slower electron transfer rates with adsorbed As(III). Results from this study offer an explanation regarding the experimental observations of Mn(III) accumulation on birnessite and the long residence time of As(III) adsorption complexes on manganite (r-MnOOH) during As(III) oxidation.

Detection and Characterization of Reactive Oxygen and Nitrogen Species in Biological Systems by Monitoring Species-Specific Products.

PubMed

Hardy, Micael; Zielonka, Jacek; Karoui, Hakim; Sikora, Adam; Michalski, Radosław; Podsiadły, Radosław; Lopez, Marcos; Vasquez-Vivar, Jeannette; Kalyanaraman, Balaraman; Ouari, Olivier

2018-05-20

Since the discovery of the superoxide dismutase enzyme, the generation and fate of short-lived oxidizing, nitrosating, nitrating, and halogenating species in biological systems has been of great interest. Despite the significance of reactive oxygen species (ROS) and reactive nitrogen species (RNS) in numerous diseases and intracellular signaling, the rigorous detection of ROS and RNS has remained a challenge. Recent Advances: Chemical characterization of the reactions of selected ROS and RNS with electron paramagnetic resonance (EPR) spin traps and fluorescent probes led to the establishment of species-specific products, which can be used for specific detection of several forms of ROS and RNS in cell-free systems and in cultured cells in vitro and in animals in vivo. Profiling oxidation products from the ROS and RNS probes provides a rigorous method for detection of those species in biological systems. Formation and detection of species-specific products from the probes enables accurate characterization of the oxidative environment in cells. Measurement of the total signal (fluorescence, chemiluminescence, etc.) intensity does not allow for identification of the ROS/RNS formed. It is critical to identify the products formed by using chromatographic or other rigorous techniques. Product analyses should be accompanied by monitoring of the intracellular probe level, another factor controlling the yield of the product(s) formed. More work is required to characterize the chemical reactivity of the ROS/RNS probes, and to develop new probes/detection approaches enabling real-time, selective monitoring of the specific products formed from the probes. Antioxid. Redox Signal. 28, 1416-1432.

Adsorption and separation of reactive aromatic isomers and generation and stabilization of their radicals within cadmium(II)-triazole metal-organic confined space in a single-crystal-to-single-crystal fashion.

PubMed

Liu, Qi-Kui; Ma, Jian-Ping; Dong, Yu-Bin

2010-05-26

A series of reactive group functionalized aromatics, namely 2-furaldehyde, 3-furaldehyde, 2-thenaldehyde, 3-thenaldehyde, o-toluidine, m-toluidine, p-toluidine, and aniline, can be absorbed by a CdL(2) (1; L = 4-amino-3,5-bis(4-pyridyl-3-phenyl)-1,2,4-triazole) porous framework in both vapor and liquid phases to generate new G(n) [symbol: see text] CdL(2) (n = 1, 2) host-guest complexes. In addition, the CdL(2) framework can be a shield to protect the active functional group (-CHO and -NH(2)) substituted guests from reaction with the outside medium containing their reaction partners. That is, aldehyde-substituted guests within the CdL(2) host become "stable" in the aniline phase and vice versa. Moreover, 1 displays a very strict selectivity for these reactive group substituted aromatic isomers and can completely separate these guest isomers under mild conditions (i.e., 2-furaldehyde vs 3-furaldehyde, 2-thenaldehyde vs 3-thenaldehyde, and o-toluidine vs m-toluidine vs p-toluidine). All adsorptions and separations are directly performed on the single crystals of 1. More interestingly, these reactive group substituted aromatics readily transform to the corresponding radicals within the CdL(2) host upon ambient light or UV light (355 nm) irradiation. Furthermore, the generated organic radicals are alive for 1 month within the interior cavity in air under ambient conditions. Simple organic radicals are highly reactive short-lived species, and they cannot be generally isolated and conserved under ambient conditions. Thus, the CdL(2) host herein could be considered as a radical generator and storage vessel.

Macroscopic and spectroscopic investigations of the adsorption of nitroaromatic compounds on graphene oxide, reduced graphene oxide, and graphene nanosheets.

PubMed

Chen, Xiaoxiao; Chen, Baoliang

2015-05-19

The surface properties and adsorption mechanisms of graphene materials are important for potential environmental applications. The adsorption of m-dinitrobenzene, nitrobenzene, and p-nitrotoluene onto graphene oxide (GO), reduced graphene oxide (RGO), and graphene (G) nanosheets was investigated using IR spectroscopy to probe the molecular interactions of graphene materials with nitroaromatic compounds (NACs). The hydrophilic GO displayed the weakest adsorption capability. The adsorption of RGO and G was significantly increased due to the recovery of hydrophobic π-conjugation carbon atoms as active sites. RGO nanosheets, which had more defect sites than did GO or G nanosheets, resulted in the highest adsorption of NACs which was 10-50 times greater than the reported adsorption of carbon nanotubes. Superior adsorption was dominated by various interaction modes including π-π electron donor-acceptor interactions between the π-electron-deficient phenyls of the NACs and the π-electron-rich matrix of the graphene nanosheets, and the charge electrostatic and polar interactions between the defect sites of graphene nanosheets and the -NO2 of the NAC. The charge transfer was initially proved by FTIR that a blue shift of asymmetric -NO2 stretching was observed with a concomitant red shift of symmetric -NO2 stretching after m-dinitrobenzene was adsorbed. The multiple interaction mechanisms of the adsorption of NAC molecule onto flat graphene nanosheets favor the adsorption, detection, and transformation of explosives.

Molecular Insights into the pH-Dependent Adsorption and Removal of Ionizable Antibiotic Oxytetracycline by Adsorbent Cyclodextrin Polymers

PubMed Central

Zhang, Yu; Cai, Xiyun; Xiong, Weina; Jiang, Hao; Zhao, Haitong; Yang, Xianhai; Li, Chao; Fu, Zhiqiang; Chen, Jingwen

2014-01-01

Effects of pH on adsorption and removal efficiency of ionizable organic compounds (IOCs) by environmental adsorbents are an area of debate, because of its dual mediation towards adsorbents and adsorbate. Here, we probe the pH-dependent adsorption of ionizable antibiotic oxytetracycline (comprising OTCH2 +, OTCH±, OTC−, and OTC2−) onto cyclodextrin polymers (CDPs) with the nature of molecular recognition and pH inertness. OTCH± commonly has high adsorption affinity, OTC− exhibits moderate affinity, and the other two species have negligible affinity. These species are evidenced to selectively interact with structural units (e.g., CD cavity, pore channel, and network) of the polymers and thus immobilized onto the adsorbents to different extents. The differences in adsorption affinity and mechanisms of the species account for the pH-dependent adsorption of OTC. The mathematical equations are derived from the multiple linear regression (MLR) analysis of quantitatively relating adsorption affinity of OTC at varying pH to adsorbent properties. A combination of the MLR analysis for OTC and molecular recognition of adsorption of the species illustrates the nature of the pH-dependent adsorption of OTC. Based on this finding, γ-HP-CDP is chosen to adsorb and remove OTC at pH 5.0 and 7.0, showing high removal efficiency and strong resistance to the interference of coexisting components. PMID:24465975

Preliminary investigation of phosphorus adsorption onto two types of iron oxide-organic matter complexes.

PubMed

Yan, Jinlong; Jiang, Tao; Yao, Ying; Lu, Song; Wang, Qilei; Wei, Shiqiang

2016-04-01

Iron oxide (FeO) coated by natural organic matter (NOM) is ubiquitous. The associations of minerals with organic matter (OM) significantly changes their surface properties and reactivity, and thus affect the environmental fate of pollutants, including nutrients (e.g., phosphorus (P)). In this study, ferrihydrite/goethite-humic acid (FH/GE-HA) complexes were prepared and their adsorption characteristics on P at various pH and ionic strength were investigated. The results indicated that the FeO-OM complexes showed a decreased P adsorption capacity in comparison with bare FeO. The maximum adsorption capacity (Qmax) decreased in the order of FH (22.17 mg/g)>FH-HA (5.43 mg/g)>GE (4.67 mg/g)>GE-HA (3.27 mg/g). After coating with HA, the amorphous FH-HA complex still showed higher P adsorption than the crystalline GE-HA complex. The decreased P adsorption observed might be attributed to changes of the FeO surface charges caused by OM association. The dependence of P adsorption on the specific surface area of adsorbents suggests that the FeO component in the complexes is still the main contributor for the adsorption surfaces. The P adsorptions on FeO-HA complexes decreased with increasing initial pH or decreasing initial ionic strength. A strong dependence of P adsorption on ionic strength and pH may demonstrate that outer-sphere complexes between the OM component on the surface and P possibly coexist with inner-sphere surface complexes between the FeO component and P. Therefore, previous over-emphasis on the contributions of original minerals to P immobilization possibly over-estimates the P loading capacity of soils, especially in humic-rich areas. Copyright © 2015. Published by Elsevier B.V.

Reaction-based small-molecule fluorescent probes for chemoselective bioimaging

PubMed Central

Chan, Jefferson; Dodani, Sheel C.; Chang, Christopher J.

2014-01-01

The dynamic chemical diversity of elements, ions and molecules that form the basis of life offers both a challenge and an opportunity for study. Small-molecule fluorescent probes can make use of selective, bioorthogonal chemistries to report on specific analytes in cells and in more complex biological specimens. These probes offer powerful reagents to interrogate the physiology and pathology of reactive chemical species in their native environments with minimal perturbation to living systems. This Review presents a survey of tools and tactics for using such probes to detect biologically important chemical analytes. We highlight design criteria for effective chemical tools for use in biological applications as well as gaps for future exploration. PMID:23174976

Enhanced adsorption of humic acids on ordered mesoporous carbon compared with microporous activated carbon.

PubMed

Liu, Fengling; Xu, Zhaoyi; Wan, Haiqin; Wan, Yuqiu; Zheng, Shourong; Zhu, Dongqiang

2011-04-01

Humic acids are ubiquitous in surface and underground waters and may pose potential risk to human health when present in drinking water sources. In this study, ordered mesoporous carbon was synthesized by means of a hard template method and further characterized by X-ray diffraction, N2 adsorption, transition electron microscopy, elemental analysis, and zeta-potential measurement. Batch experiments were conducted to evaluate adsorption of two humic acids from coal and soil, respectively, on the synthesized carbon. For comparison, a commercial microporous activated carbon and nonporous graphite were included as additional adsorbents; moreover, phenol was adopted as a small probe adsorbate. Pore size distribution characterization showed that the synthesized carbon had ordered mesoporous structure, whereas the activated carbon was composed mainly of micropores with a much broader pore size distribution. Accordingly, adsorption of the two humic acids was substantially lower on the activated carbon than on the synthesized carbon, because of the size-exclusion effect. In contrast, the synthesized carbon and activated carbon showed comparable adsorption for phenol when the size-exclusion effect was not in operation. Additionally, we verified by size-exclusion chromatography studies that the synthesized carbon exhibited greater adsorption for the large humic acid fraction than the activated carbon. The pH dependence of adsorption on the three carbonaceous adsorbents was also compared between the two test humic acids. The findings highlight the potential of using ordered mesoporous carbon as a superior adsorbent for the removal of humic acids. Copyright © 2011 SETAC.

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.

Selective turn-on fluorescent probes for imaging hydrogen sulfide in living cells.

PubMed

Montoya, Leticia A; Pluth, Michael D

2012-05-16

Hydrogen sulfide (H(2)S) is an important biological messenger but few biologically-compatible methods are available for its detection. Here we report two bright fluorescent probes that are selective for H(2)S over cysteine, glutathione and other reactive sulfur, nitrogen, and oxygen species. Both probes are demonstrated to detect H(2)S in live cells. This journal is © The Royal Society of Chemistry 2012

Adsorption and oxidation of oxalic acid on anatase TiO2 (001) surface: A density functional theory study.

PubMed

Sun, Tao; Wang, Yun; Zhang, Haimin; Liu, Porun; Zhao, Huijun

2015-09-15

Anatase TiO2 (001) surfaces have attracted great interest for photo-degradation of organic species recently due to their high reactivity. In this work, adsorption properties and oxidation mechanisms of oxalic acid on the anatase TiO2 (001) surface have been theoretically investigated using the first-principles density functional theory. Various possible adsorption configurations are considered by diversifying the connectivity of carboxylic groups with the surface. It is found that the adsorption of oxalic acid on the anatase (001) surface prefer the dissociative states. A novel double-bidentate configuration has been found due to the structural match between oxalic acid and the (001) surface. More charge is transferred from the adsorbed oxalic acid to the surface with the double-bidentate configuration when comparing with other adsorption structures. Thus, there is a positive correlation relationship between the transferred charge amount and the interfacial bond numbers when oxalic acid adsorbs on the anatase TiO2 (001) surface. The adsorption energies with dispersion corrections have demonstrated that the van der Waals interactions play an important role in the adsorption, especially when adsorbates are close to the surface. Copyright © 2015 Elsevier Inc. All rights reserved.

Cross-reactive antigens and lectin as determinants of symbiotic specificity in the Rhizobium-clover association.

PubMed Central

Dazzo, F B; Hubbell, D H

1975-01-01

Cross-reactive antigens of clover roots and Rhizobium trifolii were detected on their cell surfaces by tube agglutination, immunofluorescent, and radioimmunoassay techniques. Anti-clover root antiserum had a higher agglutinating titer with infective strains of R. trifolii than with noninfective strains. The root antiserum previously adsorbed with noninfective R. trifolii cells remained reactive only with infective cells, including infective revertants. When adsorbed with infective cells, the root antiserum was reactive with neither infective nor noninfective cells. Other Rhizobium species incapable of infecting clover did not demonstrate surface antigens cross-reactive with clover. Radioimmunoassay indicated twice as much antigenic cross-reactivity of clover roots and R. trifolii 403 (infective) than R. trifolii Bart A (noninfective). Immunofluorescence with anti-R. trifolii (infective) antiserum was detected on the exposed surface of the root epidermal cells and diminished at the root meristem. The immunofluorescent crossreaction on clover roots was totally removed by adsorption of anti-R. trifolii (infective) antiserum with encapsulated infective cells but not with noninfective cells. The cross-reactive capsular antigens from R. trifolii strains were extracted and purified. The ability of these antigens to induce clover root hair deformation was much greater when they were obtained from the infective than noninfective strains. The cross-reactive capsular antigen of R. trifolii 403 was characterized as a high-molecular-weight (greater than 4.6 times 10(6) daltons), beta-linked, acidic heteropolysaccharide containing 2-deoxyglucose, galactose, glucose, and glucuronic acid. A soluble, nondialyzable, substance (clover lectin) capable of binding to the cross-reactive antigen and agglutinating only infective cells of R. trifolii was extracted from white clover seeds. This lectin was sensitive to heat, Pronase, and trypsin. inhibition studies indicated that 2

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.

Mechanism and energetics of O and O{sub 2} adsorption on polar and non-polar ZnO surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gorai, Prashun; Seebauer, Edmund G.; Ertekin, Elif, E-mail: ertekin@illinois.edu

2016-05-14

Polar surfaces of semiconducting metal oxides can exhibit structures and chemical reactivities that are distinct from their non-polar surfaces. Using first-principles calculations, we examine O adatom and O{sub 2} molecule adsorption on 8 different known ZnO reconstructions including Zn-terminated (Zn–ZnO) and O-terminated (O–ZnO) polar surfaces, and non-polar surfaces. We find that adsorption tendencies are largely governed by the thermodynamic environment, but exhibit variations due to the different surface chemistries of various reconstructions. The Zn–ZnO surface reconstructions which appear under O-rich and H-poor environments are found to be most amenable to O and O{sub 2} adsorption. We attribute this to themore » fact that on Zn–ZnO, the O-rich environments that promote O adsorption also simultaneously favor reconstructions that involve adsorbed O species. On these Zn–ZnO surfaces, O{sub 2} dissociatively adsorbs to form O adatoms. By contrast, on O–ZnO surfaces, the O-rich conditions required for O or O{sub 2} adsorption tend to promote reconstructions involving adsorbed H species, making further O species adsorption more difficult. These insights about O{sub 2} adsorption on ZnO surfaces suggest possible design rules to understand the adsorption properties of semiconductor polar surfaces.« less

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species

NASA Astrophysics Data System (ADS)

Watts, Richard J.; Yu, Miao; Teel, Amy L.

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical + sulfate radical probe, and hexachloroethane as a reductant + nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole > > TCE > PCE > > nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion.

Reactive oxygen species and associated reactivity of peroxymonosulfate activated by soluble iron species.

PubMed

Watts, Richard J; Yu, Miao; Teel, Amy L

2017-10-01

The activation of peroxymonosulfate by iron (II), iron (III), and iron (III)-EDTA for in situ chemical oxidation (ISCO) was compared using nitrobenzene as a hydroxyl radical probe, anisole as a hydroxyl radical+sulfate radical probe, and hexachloroethane as a reductant+nucleophile probe. In addition, activated peroxymonosulfate was investigated for the treatment of the model groundwater contaminants perchloroethylene (PCE) and trichloroethylene (TCE). The relative activities of hydroxyl radical and sulfate radical in the degradation of the probe compounds and PCE and TCE were isolated using the radical scavengers tert-butanol and isopropanol. Iron (II), iron (III), and iron (III)-EDTA effectively activated peroxymonosulfate to generate hydroxyl radical and sulfate radical, but only a minimal flux of reductants or nucleophiles. Iron (III)-EDTA was a more effective activator than iron (II) and iron (III), and also provided a non-hydroxyl radical, non-sulfate radical degradation pathway. The contribution of sulfate radical relative to hydroxyl radical followed the order of anisole>TCE>PCE >nitrobenzene; i.e., sulfate radical was less dominant in the oxidation of more oxidized target compounds. Sulfate radical is often assumed to be the primary oxidant in activated peroxymonosulfate and persulfate systems, but the results of this research demonstrate that the reactivity of sulfate radical with the target compound must be considered before drawing such a conclusion. Published by Elsevier B.V.

Adsorption mechanism of acids and bases in reversed-phase liquid chromatography in weak buffered mobile phases designed for liquid chromatography/mass spectrometry.

PubMed

Gritti, Fabrice; Guiochon, Georges

2009-03-06

The overloaded band profiles of five acido-basic compounds were measured, using weakly buffered mobile phases. Low buffer concentrations were selected to provide a better understanding of the band profiles recorded in LC/MS analyses, which are often carried out at low buffer concentrations. In this work, 10 microL samples of a 50 mM probe solution were injected into C(18)-bonded columns using a series of five buffered mobile phases at (SW)pH between 2 and 12. The retention times and the shapes of the bands were analyzed based on thermodynamic arguments. A new adsorption model that takes into account the simultaneous adsorption of the acidic and the basic species onto the endcapped adsorbent, predicts accurately the complex experimental profiles recorded. The adsorption mechanism of acido-basic compounds onto RPLC phases seems to be consistent with the following microscopic model. No matter whether the acid or the base is the neutral or the basic species, the neutral species adsorbs onto a large number of weak adsorption sites (their saturation capacity is several tens g/L and their equilibrium constant of the order of 0.1 L/g). In contrast, the ionic species adsorbs strongly onto fewer active sites (their saturation capacity is about 1g/L and their equilibrium constant of the order of a few L/g). From a microscopic point of view and in agreement with the adsorption isotherm of the compound measured by frontal analysis (FA) and with the results of Monte-Carlo calculations performed by Schure et al., the first type of adsorption sites are most likely located in between C(18)-bonded chains and the second type of adsorption sites are located deeper in contact with the silica surface. The injected concentration (50 mM) was too low to probe the weakest adsorption sites (saturation capacity of a few hundreds g/L with an equilibrium constant of one hundredth of L/g) that are located at the very interface between the C(18)-bonded layer and the bulk phase.

Controls on the surface chemical reactivity of volcanic ash investigated with probe gases

NASA Astrophysics Data System (ADS)

Maters, Elena C.; Delmelle, Pierre; Rossi, Michel J.; Ayris, Paul M.; Bernard, Alain

2016-09-01

Increasing recognition that volcanic ash emissions can have significant impacts on the natural and human environment calls for a better understanding of ash chemical reactivity as mediated by its surface characteristics. However, previous studies of ash surface properties have relied on techniques that lack the sensitivity required to adequately investigate them. Here we characterise at the molecular monolayer scale the surfaces of ash erupted from Eyjafjallajökull, Tungurahua, Pinatubo and Chaitén volcanoes. Interrogation of the ash with four probe gases, trimethylamine (TMA; N(CH3)3), trifluoroacetic acid (TFA; CF3COOH), hydroxylamine (HA; NH2OH) and ozone (O3), reveals the abundances of acid-base and redox sites on ash surfaces. Measurements on aluminosilicate glass powders, as compositional proxies for the primary constituent of volcanic ash, are also conducted. We attribute the greater proportion of acidic and oxidised sites on ash relative to glass surfaces, evidenced by comparison of TMA/TFA and HA/O3 uptake ratios, in part to ash interaction with volcanic gases and condensates (e.g., H2O, SO2, H2SO4, HCl, HF) during the eruption. The strong influence of ash surface processing in the eruption plume and/or cloud is further supported by particular abundances of oxidised and reduced sites on the ash samples resulting from specific characteristics of their eruptions of origin. Intense interaction with water vapour may result in a higher fraction of oxidised sites on ash produced by phreatomagmatic than by magmatic activity. This study constitutes the first quantification of ash chemical properties at the molecular monolayer scale, and is an important step towards better understanding the factors that govern the role of ash as a chemical agent within atmospheric, terrestrial, aquatic or biotic systems.

Oxalate-curcumin-based probe for micro- and macroimaging of reactive oxygen species in Alzheimer's disease.

PubMed

Yang, Jian; Zhang, Xueli; Yuan, Peng; Yang, Jing; Xu, Yungen; Grutzendler, Jaime; Shao, Yihan; Moore, Anna; Ran, Chongzhao

2017-11-21

Alzheimer's disease (AD) is an irreversible neurodegenerative disorder that has a progression that is closely associated with oxidative stress. It has long been speculated that the reactive oxygen species (ROS) level in AD brains is much higher than that in healthy brains. However, evidence from living beings is scarce. Inspired by the "chemistry of glow stick," we designed a near-IR fluorescence (NIRF) imaging probe, termed CRANAD-61, for sensing ROS to provide evidence at micro- and macrolevels. In CRANAD-61, an oxalate moiety was utilized to react with ROS and to consequentially produce wavelength shifting. Our in vitro data showed that CRANAD-61 was highly sensitive and rapidly responsive to various ROS. On reacting with ROS, its excitation and emission wavelengths significantly shifted to short wavelengths, and this shifting could be harnessed for dual-color two-photon imaging and transformative NIRF imaging. In this report, we showed that CRANAD-61 could be used to identify "active" amyloid beta (Aβ) plaques and cerebral amyloid angiopathy (CAA) surrounded by high ROS levels with two-photon imaging (microlevel) and to provide relative total ROS concentrations in AD brains via whole-brain NIRF imaging (macrolevel). Lastly, we showed that age-related increases in ROS levels in AD brains could be monitored with our NIRF imaging method. We believe that our imaging with CRANAD-61 could provide evidence of ROS at micro- and macrolevels and could be used for monitoring ROS changes under various AD pathological conditions and during drug treatment.

Water adsorption on goethite: Application of multilayer adsorption models

NASA Astrophysics Data System (ADS)

Hatch, C. D.; Tumminello, R.; Meredith, R.

2016-12-01

Adsorbed water on the surface of atmospheric mineral dust has recently been shown to significantly affect the ability of mineral dust aerosol to act as cloud condensation nuclei. We have studied water adsorption as a function of relative humidity (RH) on goethite (α-FeO(OH)), a common component of atmospheric mineral dust. The goethite surface area and particle size was determined using BET analysis and with N2 as an adsorbate and scanning electron microscopy, respectively. Water adsorption on the sample was monitored using horizontal attenuated total reflectance Fourier transform infrared (HATR-FTIR) spectroscopy equipped with a flow cell. Water content was determined using Beer's law and the optical constants for bulk water. The results were analyzed using Type II adsorption isotherms to model multilayer adsorption, including BET (Brunauer, Emmet and Teller), FHH (Frenkel, Halsey and Hill) and Freundlich. BET fits to experimental data provide parameters of monolayer coverage, while the FHH and Freundlich isotherms provide insights into multilayer adsorption mechanisms. Results indicate that goethite contains 5% H2O by mass at 50% RH, which increases to 12% by mass at 90% RH. Adsorption parameters and experimental results will be presented.

Effect Of Reaction Environments On The Reactivity Of PCB (2-Chlorobiphenyl) Over Activated Carbon Impregnated With Palladized Iron

EPA Science Inventory

Reactive activated carbon (RAC) impregnated with palladized iron nanoparticles has been developed to treat polychlorinated biphenyls (PCBs). In this study, we evaluated the effects of various reaction environments on the adsorption-mediated dechlorination of 2-chlorobiphenyl (2-...

Enhanced removal of azo dye using modified PAN nanofibrous membrane Fe complexes with adsorption/visible-driven photocatalysis bifunctional roles

NASA Astrophysics Data System (ADS)

Li, Fu; Dong, Yongchun; Kang, Weimin; Cheng, Bowen; Cui, Guixin

2017-05-01

A series of polyacrylonitrile (PAN) nanofibrous membrane Fe complexes as the Fenton heterogeneous catalysts were fabricated through surface modification with different ratio of hydrazine hydrate (HH) and hydroxylamine (HA) and subsequent coordination with Fe3+ ions for the synergistic removal of a typical azo dye, Reactive Red 195 (RR 195) via adsorption and visible-driven photocatalytic oxidation. Effect of molar ratio of HH and HA on surface structure characteristics of the resulting complexes were examined. Their adsorptive or photocatalytic activity was also compared by changing molar ratio of HH and HA. The results indicated that three PAN nanofibrous membrane Fe complexes prepared with simultaneous modification of HA and HH exhibited much higher adsorption and visible photocatalytic activities than the complex modified solely with HA or HH due to their distinctive surface structures containing more active sites. Their adsorption and visible photocatalytic kinetics of RR 195 followed pseudo-second-order model equation. Their high photocatalytic rate constant and large amount of dye adsorption were regarded as the main reasons for better dye removal efficiency and durability in cyclic reuse by means of the synergistic adsorption-photocatalysis process.

ATR-FTIR Spectroscopy in the Undergraduate Chemistry Laboratory: Part II--A Physical Chemistry Laboratory Experiment on Surface Adsorption

ERIC Educational Resources Information Center

Schuttlefield, Jennifer D.; Larsen, Sarah C.; Grassian, Vicki H.

2008-01-01

Attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy is a useful technique for measuring the infrared spectra of solids and liquids as well as probing adsorption on particle surfaces. The use of FTIR-ATR spectroscopy in organic and inorganic chemistry laboratory courses as well as in undergraduate research was presented…

Oxidation of tertiary amines by cytochrome p450-kinetic isotope effect as a spin-state reactivity probe.

PubMed

Li, Chunsen; Wu, Wei; Cho, Kyung-Bin; Shaik, Sason

2009-08-24

Two types of tertiary amine oxidation processes, namely, N-dealkylation and N-oxygenation, by compound I (Cpd I) of cytochrome P450 are studied theoretically using hybrid DFT calculations. All the calculations show that both N-dealkylation and N-oxygenation of trimethylamine (TMA) proceed preferentially from the low-spin (LS) state of Cpd I. Indeed, the computed kinetic isotope effects (KIEs) for the rate-controlling hydrogen abstraction step of dealkylation show that only the KIE(LS) fits the experimental datum, whereas the corresponding value for the high-spin (HS) process is much higher. These results second those published before for N,N-dimethylaniline (DMA), and as such, they further confirm the conclusion drawn then that KIEs can be a sensitive probe of spin state reactivity. The ferric-carbinolamine of TMA decomposes most likely in a non-enzymatic reaction since the Fe-O bond dissociation energy (BDE) is negative. The computational results reveal that in the reverse reaction of N-oxygenation, the N-oxide of aromatic amine can serve as a better oxygen donor than that of aliphatic amine to generate Cpd I. This capability of the N-oxo derivatives of aromatic amines to transfer oxygen to the heme, and thereby generate Cpd I, is in good accord with experimental data previously reported.

A benzothiazole-based fluorescent probe for hypochlorous acid detection and imaging in living cells

NASA Astrophysics Data System (ADS)

Nguyen, Khac Hong; Hao, Yuanqiang; Zeng, Ke; Fan, Shengnan; Li, Fen; Yuan, Suke; Ding, Xuejing; Xu, Maotian; Liu, You-Nian

2018-06-01

A benzothiazole-based turn-on fluorescent probe with a large Stokes shift (190 nm) has been developed for hypochlorous acid detection. The probe displays prompt fluorescence response for HClO with excellent selectivity over other reactive oxygen species as well as a low detection limit of 0.08 μM. The sensing mechanism involves the HClO-induced specific oxidation of oxime moiety of the probe to nitrile oxide, which was confirmed by HPLC-MS technique. Furthermore, imaging studies demonstrated that the probe is cell permeable and can be applied to detect HClO in living cells.

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

The construction, characterization, Hg(II)-sensing and removal behavior of magnetic core-shell nanospheres loaded with fluorescence "Off-On" probe

NASA Astrophysics Data System (ADS)

Tan, Jun; Wei, Xiaoyan; Chen, Jie; Sun, Ping; Ouyang, Yuxia; Fan, Juhong; Liu, Rui

2014-12-01

The present paper constructed and discussed core-shell structured nanospheres grafted with rhodamine based probe for Hg(II) sensing and removal. Electron microscopy images, XRD curves, thermogravimetric analysis and N2 adsorption/desorption isotherms were used to identify the core-shell structure. The inner core consisted of superparamagnetic Fe3O4 nanoparticles, which made the nanocomposite magnetically removable. The outer shell was constructed with silica molecular sieve which provided large surface area and ordered tunnels for the sensing probe, accelerating analyte adsorption and transportation. The rhodamine based sensing probe emission increased with the increasing Hg(II) concentration, showing emission "Off-On" effect, which could be explained by the structural transformation from a non-emissive one to a highly emissive one. The influence from various metal ions and pH values was also investigated, which suggested this structural transformation could only be triggered by Hg(II), showing high selectivity and linear response. The Hg(II) sensing nanocomposite could be regenerated after usage. The response time was slightly compromised and could be further improved.

A simple rhodamine hydrazide-based turn-on fluorescent probe for HOCl detection.

PubMed

Zhang, Zhen; Zou, Yuan; Deng, Chengquan; Meng, Liesu

2016-06-01

Hypochlorous acid (HOCl) plays a crucial role in daily life and mediates a variety of physiological processes, however, abnormal levels of HOCl have been associated with numerous human diseases. It is therefore of significant interest to establish a simple, selective, rapid and sensitive fluorogenic method for the detection of HOCl in environmental and biological samples. A hydrazide-containing fluorescent probe based on a rhodamine scaffold was facilely developed that could selectively detect HOCl over other biologically relevant reactive oxygen species, reactive nitrogen species and most common metal ions in vitro. Via an irreversible oxidation-hydrolysis mechanism, and upon HOCl-triggered opening of the intramolecular spirocyclic ring during detection, the rhodamine hydrazide-based probe exhibited large fluorescence enhancement in the emission spectra with a fast response, low detection limit and comparatively wide pH detection range in aqueous media. The probe was further successfully applied to monitoring trace HOCl in tap water and imaging both exogenous and endogenous HOCl within living cells. It is anticipated that this simple and useful probe might be an efficient tool with which to facilitate more HOCl-related chemical and biological research. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Nanoparticle forming reactive plasmas: a multidiagnostic approach

NASA Astrophysics Data System (ADS)

Hinz, Alexander; Wahl, Erik von; Faupel, Franz; Strunskus, Thomas; Kersten, Holger

2018-05-01

With an ever increasing interest in functional materials based on nanoparticles a large amount of research in this field is dedicated to the development of new production methods for nanoparticles. A promising class of methods for the production of nanoparticles is reactive plasmas. However, since the particle formation process and the interaction between the particles and the plasma are so far not completely understood, it remains difficult to control the particle formation. As the interaction between the nanoparticles and the plasma in which they are dispersed is complex the use of one or two diagnostics often provides only an incomplete understanding of the involved processes. Thus a multidiagnostic approach is needed. This contribution reviews the latest results from the study of nanoparticle formation in a hydrocarbon-based reactive plasma by such a multidiagnostic approach. It is shown that the use of various diagnostics like an IV-probe, optical emission spectroscopy, and a multipole resonance probe in conjunction with an investigation of the particle formation provides a much more detailed picture of these interesting, yet challenging, systems. Contribution to the Topical Issue "Fundamentals of Complex Plasmas", edited by Jürgen Meichsner, Michael Bonitz, Holger Fehske, Alexander Piel.

Adsorption Refrigeration System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Kai; Vineyard, Edward Allan

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 drawbacksmore » 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.« less

Adsorption of methanol, ethanol and water on well-characterized PtSn surface alloys

NASA Astrophysics Data System (ADS)

Panja, Chameli; Saliba, Najat; Koel, Bruce E.

1998-01-01

Adsorption and desorption of methanol (CH 3OH), ethanol (C 2H 5OH) and water on Pt(111) and two, ordered, PtSn alloys has been studied primarily using temperature-programmed desorption (TPD) mass spectroscopy. The two alloys studied were the {p(2 × 2) Sn}/{Pt(111) } and (√3 × √3) R30° {Sn}/{Pt(111) } surface alloys prepared by vapor deposition of Sn on Pt(111), with θSn = 0.25 and 0.33, respectively. All three molecules are weakly bonded and reversibly adsorbed under UHV conditions on all three surfaces, molecularly desorbing during TPD without any decomposition. The two PtSn surface alloys were found to chemisorb both methanol and ethanol slightly more weakly than on the Pt(111) surface. The desorption activation energies measured by TPD, and hence the adsorption energies, of both methanol and ethanol progressively decrease as the surface concentration of Sn increases, compared with Pt(111). The decreased binding energy leads one to expect a lower reactivity for these alcohols on the two alloys. The sticking coefficients and the monolayer coverages of these alcohols on the two alloys were identical to that on Pt(111) at 100 K, independent of the amount of Sn present in the surface layer. Alloying Sn in Pt(111) also slightly weakens the adsorption energy of water. Water clusters are formed even at low coverages on all three surfaces, eventually forming a water bilayer prior to the formation of a condensed ice phase. These results are relevant to a molecular-level explanation for the reactivity of Sn-promoted Pt surfaces that have been used in the electro-oxidation of simple organic molecules.

Al atom on MoO3(010) surface: adsorption and penetration using density functional theory.

PubMed

Wu, Hong-Zhang; Bandaru, Sateesh; Wang, Da; Liu, Jin; Lau, Woon Ming; Wang, Zhenling; Li, Li-Li

2016-03-14

Interfacial issues, such as the interfacial structure and the interdiffusion of atoms at the interface, are fundamental to the understanding of the ignition and reaction mechanisms of nanothermites. This study employs first-principle density functional theory to model Al/MoO3 by placing an Al adatom onto a unit cell of a MoO3(010) slab, and to probe the initiation of interfacial interactions of Al/MoO3 nanothermite by tracking the adsorption and subsurface-penetration of the Al adatom. The calculations show that the Al adatom can spontaneously go through the topmost atomic plane (TAP) of MoO3(010) and reach the 4-fold hollow adsorption-site located below the TAP, with this subsurface adsorption configuration being the most preferred one among all plausible adsorption configurations. Two other plausible configurations place the Al adatom at two bridge sites located above the TAP of MoO3(010) but the Al adatom can easily penetrate below this TAP to a relatively more stable adsorption configuration, with a small energy barrier of merely 0.2 eV. The evidence of subsurface penetration of Al implies that Al/MoO3 likely has an interface with intermixing of Al, Mo and O atoms. These results provide new insights on the interfacial interactions of Al/MoO3 and the ignition/combustion mechanisms of Al/MoO3 nanothermites.

Adsorption of dissolved organics in lake water by aluminum oxide. Effect of molecular weight

USGS Publications Warehouse

Davis, J.A.; Gloor, R.

1981-01-01

Dissolved organic compounds in a Swiss lake were fractionated into three molecular size classes by gel exclusion chromatography, and adsorption of each fraction on colloidal alumina was studied as a function of pH. Organic compounds with molecular weight (Mr) greater than 1000 formed strong complexes with the alumina surface, but low molecular weight compounds were weakly adsorbed. Electrophoretic mobility measurements indicated that alumina particles suspended in the original lake water were highly negatively charged because of adsorbed organic matter. Most of the adsorbed organic compounds were in the Mr range 1000 < Mr < 3000. Adsorption of these compounds during the treatment of drinking water by alum coagulation may be responsible for the preferential removal of trihalomethane precursors. Adsorption may also influence the molecular-weight distribution of dissolved organic material in lakes. surface, the present work will focus on the influence of molecular size and pH on the adsorption behavior of dissolved organic material of a Swiss lake. From a geochemical point of view, it is important to know the molecular-weight distribution of adsorbed organic matter so that we may better assess its reactivity with trace elements. The study also serves as a first step in quantifying the role of adsorption in the geochemical cycle of organic carbon in lacustrine environments. For water-treatment practice, we need to determine whether molecular weight fractionation occurs during adsorption by aluminum oxide. Such a fractionation could be significant in the light of recent reports that chloroform and other organochlorine compounds are preferentially produced by particular molecular-weight fractions (25-27). ?? 1981 American Chemical Society.

A flow-pulse adsorption-microcalorimetry system for studies of adsorption processes on powder catalysts

NASA Astrophysics Data System (ADS)

You, Rui; Li, Zhaorui; Zeng, Hongyu; Huang, Weixin

2018-06-01

A pulse chemisorption system combining a Tian-Calvet microcalorimeter (Setaram Sensys EVO 600) and an automated chemisorption apparatus (Micromeritics Autochem II 2920) was established to accurately measure differential adsorption heats of gas molecules' chemisorption on solid surfaces in a flow-pulse mode. Owing to high sensitivity and high degree of automation in a wide range of temperatures from -100 to 600 °C, this coupled system can present adsorption heats as a function of adsorption temperature and adsorbate coverage. The functions of this system were demonstrated by successful measurements of CO adsorption heats on Pd surfaces at various temperatures and also at different CO coverages by varying the CO concentration in the pulse dose. Key parameters, including adsorption amounts, integral adsorption heats, and differential adsorption heats of CO adsorption on a Pd/CeO2 catalyst, were acquired. Our adsorption-microcalorimetry system provides a powerful technique for the investigation of adsorption processes on powder catalysts.

Apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2005-12-13

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Method for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; Stenkamp, Victoria S.; TeGrotenhuis, Ward E.; Matson, Dean W.; Drost, M. Kevin; Viswanathan, Vilayanur V.

2003-10-07

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Biosensors for spatiotemporal detection of reactive oxygen species in cells and tissues.

PubMed

Erard, Marie; Dupré-Crochet, Sophie; Nüße, Oliver

2018-05-01

Redox biology has become a major issue in numerous areas of physiology. Reactive oxygen species (ROS) have a broad range of roles from signal transduction to growth control and cell death. To understand the nature of these roles, accurate measurement of the reactive compounds is required. An increasing number of tools for ROS detection is available; however, the specificity and sensitivity of these tools are often insufficient. Furthermore, their specificity has been rarely evaluated in complex physiological conditions. Many ROS probes are sensitive to environmental conditions in particular pH, which may interfere with ROS detection and cause misleading results. Accurate detection of ROS in physiology and pathophysiology faces additional challenges concerning the precise localization of the ROS and the timing of their production and disappearance. Certain ROS are membrane permeable, and certain ROS probes move across cells and organelles. Targetable ROS probes such as fluorescent protein-based biosensors are required for accurate localization. Here we analyze these challenges in more detail, provide indications on the strength and weakness of current tools for ROS detection, and point out developments that will provide improved ROS detection methods in the future. There is no universal method that fits all situations in physiology and cell biology. A detailed knowledge of the ROS probes is required to choose the appropriate method for a given biological problem. The knowledge of the shortcomings of these probes should also guide the development of new sensors.

Homogenous and heterogenous advanced oxidation of two commercial reactive dyes.

PubMed

Balcioglu, I A; Arslan, I; Sacan, M T

2001-07-01

Two commercial reactive dyes, the azo dye Reactive Black 5 and the copper phythalocyanine dye Reactive Blue 21, have been treated at a concentration of 75 mg l(-1) by titanium dioxide mediated photocatalytic (TiO2/UV), dark and UV-light assisted Fenton (Fe2+/H2O2) and Fenton-like (Fe3+/H2O2) processes in acidic medium. For the treatment of Reactive Black 5, all investigated advanced oxidation processes were quite effective in terms of colour, COD as well as TOC removal. Moreover, the relative growth inhibition of the azo dye towards the marine algae Dunaliella tertiolecta that was initially 70%, did not exhibit an increase during the studied advanced oxidation reactions and complete detoxification at the end of the treatment period could be achieved for all investigated treatment processes. However, for Reactive Blue 21, abatement in COD and UV-VIS absorbance values was mainly due to the adsorption of the dye on the photocatalyst surface and/or the coagulative effect of Fe3+/Fe2+ ions. Although only a limited fraction of the copper phythalocyanine dye underwent oxidative degradation, 47% of the total copper in the dye was already released after 1 h photocatalytic treatment.

Initial data on adsorption of Cs and Sr to the surfaces of microplastics with biofilm.

PubMed

Johansen, Mathew P; Prentice, Emily; Cresswell, Tom; Howell, Nick

2018-10-01

The adsorption of radiocesium and radiostrontium onto a range of natural materials has been well quantified, but not for the new media of environmental plastics, which may have enhanced adsorption due to surface-weathering and development of biofilms. Microplastic samples were deployed in freshwater, estuarine and marine conditions, then characterised using infrared spectroscopy to document changes to the plastic surface (vs interior). Synchrotron elemental mapping data revealed surfaces that were well-covered by accumulation of reactive water solutes and sulphur, but, in contrast, had highly discrete coverage of elements such as Fe and Ti, indicating adhered mineral/clay-associated agglomerates that may increase overall adsorption capacity. Plastics that had been deployed for nearly five months adsorbed radionuclides in both freshwater and estuarine conditions with the highest K d for cesium (Cs) in freshwater (80 ml g -1 ) and lowest for strontium (Sr) in estuarine conditions (5 ml g -1 ). The degree of Cs and Sr adsorption onto plastics appears to be approximately 2-3 orders of magnitude lower than for sediment reference values. While lower than for sediments, adsorption occurred on all samples and may indicate a significant radionuclide reservoir, given that plastics are relatively buoyant and mobile in water regimes, and are increasing in global aquatic systems. Crown Copyright © 2018. Published by Elsevier Ltd. All rights reserved.

Experimental Study on Treatment of Dyeing Wastewater by Activated Carbon Adsorption, Coagulation and Fenton Oxidation

NASA Astrophysics Data System (ADS)

Xiaoxu, SUN; Jin, XU; Xingyu, LI

2017-12-01

In this paper dyeing waste water was simulated by reactive brilliant blue XBR, activated carbon adsorption process, coagulation process and chemical oxidation process were used to treat dyeing waste water. In activated carbon adsorption process and coagulation process, the water absorbance values were measured. The CODcr value of water was determined in Fenton chemical oxidation process. Then, the decolorization rate and COD removal rate were calculated respectively. The results showed that the optimum conditions of activated carbon adsorption process were as follows: pH=2, the dosage of activated carbon was 1.2g/L, the adsorption reaction time was 60 min, and the average decolorization rate of the three parallel experiments was 85.30%. The optimum conditions of coagulation experiment were as follows: pH=8~9, PAC dosage was 70mg/L, stirring time was 20min, standing time was 45min, the average decolorization rate of the three parallel experiments was 74.48%. The optimum conditions for Fenton oxidation were Fe2+ 0.05g/L, H2O2 (30%) 14mL/L, pH=3, reaction time 40min. The average CODcr removal rate was 69.35% in three parallel experiments. It can be seen that in the three methods the activated carbon adsorption treatment of dyeing wastewater was the best one.

Water adsorption constrained Frenkel-Halsey-Hill adsorption activation theory: Montmorillonite and illite

NASA Astrophysics Data System (ADS)

Hatch, Courtney D.; Greenaway, Ann L.; Christie, Matthew J.; Baltrusaitis, Jonas

2014-04-01

Fresh mineral aerosol has recently been found to be effective cloud condensation nuclei (CCN) and contribute to the number of cloud droplets in the atmosphere due to the effect of water adsorption on CCN activation. The work described here uses experimental water adsorption measurements on Na-montmorillonite and illite clay to determine empirical adsorption parameters that can be used in a recently derived theoretical framework (Frenkel-Halsey-Hill Activation Theory, FHH-AT) that accounts for the effect of water adsorption on CCN activation. Upon fitting the Frenkel-Halsey-Hill (FHH) adsorption model to water adsorption measurements, we find FHH adsorption parameters, AFHH and BFHH, to be 98 ± 22 and 1.79 ± 0.11 for montmorillonite and 75 ± 17 and 1.77 ± 0.11 for illite, respectively. The AFHH and BFHH values obtained from water adsorption measurements differ from values reported previously determined by applying FHH-AT to CCN activation measurements. Differences in FHH adsorption parameters were attributed to different methods used to obtain them and the hydratable nature of the clays. FHH adsorption parameters determined from water adsorption measurements were then used to calculate the critical super-saturation (sc) for CCN activation using FHH-AT. The relationship between sc and the dry particle diameter (Ddry) gave CCN activation curve exponents (xFHH) of -0.61 and -0.64 for montmorillonite and illite, respectively. The xFHH values were slightly lower than reported previously for mineral aerosol. The lower exponent suggests that the CCN activity of hydratable clays is less sensitive to changes in Ddry and the hygroscopicity parameter exhibits a broader variability with Ddry compared to more soluble aerosols. Despite the differences in AFHH, BFHH and xFHH, the FHH-AT derived CCN activities of montmorillonite and illite are quite similar to each other and in excellent agreement with experimental CCN measurements resulting from wet-generated clay aerosol

DNA-encapsulated silver nanodots as ratiometric luminescent probes for hypochlorite detection

NASA Astrophysics Data System (ADS)

Park, Soonyoung; Choi, Sungmoon; Yu, Junhua

2014-03-01

DNA-encapsulated silver nanodots are noteworthy candidates for bio-imaging probes, thanks to their excellent photophysical properties. The spectral shift of silver nanodot emitters from red to blue shows excellent correlations with the concentration of reactive oxygen species, which makes it possible to develop new types of probes for reactive oxygen species (ROS), such as hypochlorous acid (HOCl), given the outstanding stability of the blue in oxidizing environments. HOCl plays a role as a microbicide in immune systems but, on the other hand, is regarded as a disease contributor. Moreover, it is a common ingredient in household cleaners. There are still great demands to detect HOCl fluxes and their physiological pathways. We introduce a new ratiometric luminescence imaging method based on silver nanodots to sensitively detect hypochlorite. The factors that influence the accuracy of the detection are investigated. Its availability has also been demonstrated by detecting the active component in cleaners.

Probing the association between serotonin-1A autoreceptor binding and amygdala reactivity in healthy volunteers.

PubMed

Kranz, Georg S; Hahn, Andreas; Kraus, Christoph; Spies, Marie; Pichler, Verena; Jungwirth, Johannes; Mitterhauser, Markus; Wadsak, Wolfgang; Windischberger, Christian; Kasper, Siegfried; Lanzenberger, Rupert

2018-05-01

The serotonergic system modulates affect and is a target in the treatment of mood disorders. 5-HT 1A autoreceptors in the raphe control serotonin release by means of negative feedback inhibition. Hence, 5-HT 1A autoreceptor function should influence the serotonergic regulation of emotional reactivity in limbic regions. Previous findings suggest an inverse relationship between 5-HT 1A autoreceptor binding and amygdala reactivity to facial emotional expressions. The aim of the current multimodal neuroimaging study was to replicate the previous finding in a larger cohort. 31 healthy participants underwent fMRI as well as PET using the radioligand [carbonyl- 11 C]WAY-100635 to quantify 5-HT 1A autoreceptor binding in the dorsal raphe. The binding potential (BP ND ) was quantified using the multilinear reference tissue model (MRTM2) and cerebellar white matter as reference tissue. Functional MRI was done at 3T using a well-established facial emotion discrimination task (EDT). Here, participants had to match the emotional valence of facial expressions, while in a control condition they had to match geometric shapes. Effects of 5-HT 1A autoreceptor binding on amygdala reactivity were investigated using linear regression analysis with SPM8. Regression analysis between 5-HT 1A autoreceptor binding and mean amygdala reactivity revealed no statistically significant associations. Investigating amygdala reactivity in a voxel-wise approach revealed a positive association in the right amygdala (peak-T = 3.64, p < .05 FWE corrected for the amygdala volume) which was however conditional on the omission of age and sex as covariates in the model. Despite highly significant amygdala reactivity to facial emotional expressions, we were unable to replicate the inverse relationship between 5-HT 1A autoreceptor binding in the DRN and amygdala reactivity. Our results oppose previous multimodal imaging studies but seem to be in line with recent animal research. Deviation in results

Physiological correlates of emotional reactivity and regulation in early adolescents.

PubMed

Latham, Melissa D; Cook, Nina; Simmons, Julian G; Byrne, Michelle L; Kettle, Jonathan W L; Schwartz, Orli; Vijayakumar, Nandita; Whittle, Sarah; Allen, Nicholas B

2017-07-01

Few studies have examined physiological correlates of emotional reactivity and regulation in adolescents, despite the occurrence in this group of significant developmental changes in emotional functioning. The current study employed multiple physiological measures (i.e., startle-elicited eyeblink and ERP, skin conductance, facial EMG) to assess the emotional reactivity and regulation of 113 early adolescents in response to valenced images. Reactivity was measured while participants viewed images, and regulation was measured when they were asked to discontinue or maintain their emotional reactions to the images. Adolescent participants did not exhibit fear-potentiated startle blink. However, they did display affect-consistent zygomatic and corrugator activity during reactivity, as well as inhibition of some of these facial patterns during regulation. Skin conductance demonstrated arousal dependent activity during reactivity, and overall decreases during regulation. These findings suggest that early adolescents display reactivity to valenced pictures, but not to startle probes. Psychophysiological patterns during emotion regulation indicate additional effort and/or attention during the regulation process. Copyright © 2017 Elsevier B.V. All rights reserved.

Effect of oxidation and catalytic reduction of trace organic contaminants on their activated carbon adsorption.

PubMed

Schoutteten, Klaas V K M; Hennebel, Tom; Dheere, Ellen; Bertelkamp, Cheryl; De Ridder, David J; Maes, Synthia; Chys, Michael; Van Hulle, Stijn W H; Vanden Bussche, Julie; Vanhaecke, Lynn; Verliefde, Arne R D

2016-12-01

The combination of ozonation and activated carbon (AC) adsorption is an established technology for removal of trace organic contaminants (TrOCs). In contrast to oxidation, reduction of TrOCs has recently gained attention as well, however less attention has gone to the combination of reduction with AC adsorption. In addition, no literature has compared the removal behavior of reduction vs. ozonation by-products by AC. In this study, the effect of pre-ozonation vs pre-catalytic reduction on the AC adsorption efficiency of five TrOCs and their by-products was compared. All compounds were susceptible to oxidation and reduction, however the catalytic reductive treatment proved to be a slower reaction than ozonation. New oxidation products were identified for dinoseb and new reduction products were identified for carbamazepine, bromoxynil and dinoseb. In terms of compatibility with AC adsorption, the influence of the oxidative and reductive pretreatments proved to be compound dependent. Oxidation products of bromoxynil and diatrizoic acid adsorbed better than their parent TrOCs, but oxidation products of atrazine, carbamazepine and dinoseb showed a decreased adsorption. The reductive pre-treatment showed an enhanced AC adsorption for dinoseb and a major enhancement for diatrizoic acid. For atrazine and bromoxynil, no clear influence on adsorption was noted, while for carbamazepine, the reductive pretreatment resulted in a decreased AC affinity. It may thus be concluded that when targeting mixtures of TrOCs, a trade-off will undoubtedly have to be made towards overall reactivity and removal of the different constituents, since no single treatment proves to be superior to the other. Copyright © 2016 Elsevier Ltd. All rights reserved.

Electrospun polyacrylonitrile nanofibers functionalized with EDTA for adsorption of ionic dyes

NASA Astrophysics Data System (ADS)

Chaúque, Eutilério F. C.; Dlamini, Langelihle N.; Adelodun, Adedeji A.; Greyling, Corinne J.; Ngila, J. Catherine

2017-08-01

The manipulation of nanofibers' surface chemistry could enhance their potential application toward the removal of ionic dyes in wastewater. For this purpose, surface modification of electrospun polyacrylonitrile (PAN) nanofibers with ethylenediaminetetraacetic acid (EDTA) and ethylenediamine (EDA) crosslinker was experimented. The functionalized EDTA-EDA-PAN nanofibers were characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) technique. The impregnation of EDA and EDTA chelating agents on the surface of PAN changed the distribution of nanofibers as proximity is increased (accompanied by reduced softness), but the nanofibrous structure of the pristine PAN nanofibers was not substantially altered. Adsorption equilibrium studies were performed with Freundlich, Langmuir and Temkin isotherm models with the former providing better correlation to the experimental data. The modified PAN nanofibers showed efficient sorption of methyl orange (MO) and reactive red (RR) from aqueous synthetic samples, evinced by the maximum adsorption capacities (at 25 °C) of 99.15 and 110.0 mg g-1, respectively. The fabricated nanofibers showed appreciable removal efficiency of the target dye sorptives from wastewater. However, the presence of high metal ions content affected the overall extraction of dyes from wastewater due to the depletion of the adsorbent's active adsorptive sites.

Chemical probes for competitive profiling of the quorum sensing signal synthase PqsD of Pseudomonas aeruginosa

PubMed Central

Prothiwa, Michaela; Szamosvári, Dávid; Glasmacher, Sandra

2016-01-01

The human pathogen Pseudomonas aeruginosa uses the pqs quorum sensing system to coordinate the production of its broad spectrum of virulence factors to facilitate colonization and infection of its host. Hereby, the enzyme PqsD is a virulence related quorum sensing signal synthase that catalyzes the central step in the biosynthesis of the Pseudomonas quinolone signals HHQ and PQS. We developed a library of cysteine reactive chemical probes with an alkyne handle for fluorescence tagging and report the selective and highly sensitive in vitro labelling of the active site cysteine of this important enzyme. Interestingly, only one type of probe, with a reactive α-chloroacetamide was capable of covalently reacting with the active site. We demonstrated the potential of our probes in a competitive labelling platform where we screened a library of synthetic HHQ and PQS analogues with heteroatom replacements and found several inhibitors of probe binding that may represent promising scaffolds for the development of customized PqsD inhibitors as well as a chemical toolbox to investigate the activity and active site specificity of the enzyme. PMID:28144351

Reactive Oxygen Species (ROS) generation by lunar simulants

NASA Astrophysics Data System (ADS)

Kaur, Jasmeet; Rickman, Douglas; Schoonen, Martin A.

2016-05-01

The current interest in human exploration of the Moon and past experiences of Apollo astronauts has rekindled interest into the possible harmful effects of lunar dust on human health. In comparison to the Apollo-era explorations, human explorers may be weeks on the Moon, which will raise the risk of inhalation exposure. The mineralogical composition of lunar dust is well documented, but its effects on human health are not fully understood. With the aim of understanding the reactivity of dusts that may be encountered on geologically different lunar terrains, we have studied Reactive Oxygen Species (ROS) generation by a suite of lunar simulants of different mineralogical-chemical composition dispersed in water and Simulated Lung Fluid (SLF). To further explore the reactivity of simulants under lunar environmental conditions, we compared the reactivity of simulants both in air and inert atmosphere. As the impact of micrometeorites with consequent shock-induced stresses is a major environmental factor on the Moon, we also studied the effect of mechanical stress on samples. Mechanical stress was induced by hand crushing the samples both in air and inert atmosphere. The reactivity of samples after crushing was analyzed for a period of up to nine days. Hydrogen peroxide (H2O2) in water and SLF was analyzed by an in situ electrochemical probe and hydroxyl radical (•OH) by Electron Spin Resonance (ESR) spectroscopy and Adenine probe. Out of all simulants, CSM-CL-S was found to be the most reactive simulant followed by OB-1 and then JSC-1A simulant. The overall reactivity of samples in the inert atmosphere was higher than in air. Fresh crushed samples showed a higher level of reactivity than uncrushed samples. Simulant samples treated to create agglutination, including the formation of zero-valent iron, showed less reactivity than untreated simulants. ROS generation in SLF is initially slower than in deionized water (DI), but the ROS formation is sustained for as long as 7

FRET study of G-quadruplex forming fluorescent oligonucleotide probes at the lipid monolayer interface.

PubMed

Swiatkowska, Angelika; Kosman, Joanna; Juskowiak, Bernard

2016-01-05

Spectral properties and G-quadruplex folding ability of fluorescent oligonucleotide probes at the cationic dioctadecyldimethylammonium bromide (DODAB) monolayer interface are reported. Two oligonucleotides, a 19-mer bearing thrombin binding aptamer sequence and a 21-mer with human telomeric sequence, were end-labeled with fluorescent groups (FAM and TAMRA) to give FRET probes F19T and F21T, respectively. The probes exhibited abilities to fold into a quadruplex structure and to bind metal cations (Na(+) and K(+)). Fluorescence spectra of G-quadruplex FRET probes at the monolayer interface are reported for the first time. Investigations included film balance measurements (π-A isotherms) and fluorescence spectra recording using a fiber optic accessory interfaced with a spectrofluorimeter. The effect of the presence of DODAB monolayer, metal cations and the surface pressure of monolayer on spectral behavior of FRET probes were examined. Adsorption of probe at the cationic monolayer interface resulted in the FRET signal enhancement even in the absence of metal cations. Variation in the monolayer surface pressure exerted rather modest effect on the spectral properties of probes. The fluorescence energy transfer efficiency of monolayer adsorbed probes increased significantly in the presence of sodium or potassium ion in subphase, which indicated that the probes retained their cation binding properties when adsorbed at the monolayer interface. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption mechanism of acids and bases in reversed-phase liquid chromatography in weak buffered mobile phases designed for liquid chromatography/mass spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gritti, Fabrice; Guiochon, Georges A

2009-01-01

The overloaded band profiles of five acido-basic compounds were measured, using weakly buffered mobile phases. Low buffer concentrations were selected to provide a better understanding of the band profiles recorded in LC/MS analyses, which are often carried out at low buffer concentrations. In this work, 10 {micro}L samples of a 50 mM probe solution were injected into C{sub 18}-bonded columns using a series of five buffered mobile phases at {sub W}{sup S}pH between 2 and 12. The retention times and the shapes of the bands were analyzed based on thermodynamic arguments. A new adsorption model that takes into account themore » simultaneous adsorption of the acidic and the basic species onto the endcapped adsorbent, predicts accurately the complex experimental profiles recorded. The adsorption mechanism of acido-basic compounds onto RPLC phases seems to be consistent with the following microscopic model. No matter whether the acid or the base is the neutral or the basic species, the neutral species adsorbs onto a large number of weak adsorption sites (their saturation capacity is several tens g/L and their equilibrium constant of the order of 0.1 L/g). In contrast, the ionic species adsorbs strongly onto fewer active sites (their saturation capacity is about 1 g/L and their equilibrium constant of the order of a few L/g). From a microscopic point of view and in agreement with the adsorption isotherm of the compound measured by frontal analysis (FA) and with the results of Monte-Carlo calculations performed by Schure et al., the first type of adsorption sites are most likely located in between C{sub 18}-bonded chains and the second type of adsorption sites are located deeper in contact with the silica surface. The injected concentration (50 mM) was too low to probe the weakest adsorption sites (saturation capacity of a few hundreds g/L with an equilibrium constant of one hundredth of L/g) that are located at the very interface between the C{sub 18}-bonded layer and

Investigation of protein adsorption performance of Ni2+-attached diatomite particles embedded in composite monolithic cryogels.

PubMed

Ünlü, Nuri; Ceylan, Şeyda; Erzengin, Mahmut; Odabaşı, Mehmet

2011-08-01

As a low-cost natural adsorbent, diatomite (DA) (2 μm) has several advantages including high surface area, chemical reactivity, hydrophilicity and lack of toxicity. In this study, the protein adsorption performance of supermacroporous composite cryogels embedded with Ni(2+)-attached DA particles (Ni(2+)-ADAPs) was investigated. Supermacroporous poly(2-hydroxyethyl methacrylate) (PHEMA)-based monolithic composite cryogel column embedded with Ni(2+)-ADAPs was prepared by radical cryo-copolymerization of 2-hydroxyethyl methacrylate (HEMA) with N,N'-methylene-bis-acrylamide (MBAAm) as cross-linker directly in a plastic syringe for affinity purification of human serum albumin (HSA) both from aqueous solutions and human serum. The chemical composition and surface area of DA was determined by XRF and BET method, respectively. The characterization of composite cryogel was investigated by SEM. The effect of pH, and embedded Ni(2+)-ADAPs amount, initial HSA concentration, temperature and flow rate on adsorption were studied. The maximum amount of HSA adsorption from aqueous solution at pH 8.0 phosphate buffer was very high (485.15 mg/g DA). It was observed that HSA could be repeatedly adsorbed and desorbed to the embedded Ni(2+)-ADAPs in poly(2-hydroxyethyl methacrylate) composite cryogel without significant loss of adsorption capacity. The efficiency of albumin adsorption from human serum before and after albumin adsorption was also investigated with SDS-PAGE analyses. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of Drug-Induced Hepatotoxicity and Its Remediation Pathway with Reaction-Based Fluorescent Probes.

PubMed

Cheng, Dan; Xu, Wang; Yuan, Lin; Zhang, Xiaobing

2017-07-18

Drug-induced liver injury (DILI) is considered a serious problem related to public health, due to its unpredictability and acute response. The level of peroxynitrite (ONOO - ) generated in liver has long been regarded as a biomarker for the prediction and measurement of DILI. Herein we present two reaction-based fluorescent probes (Naph-ONOO - and Rhod-ONOO - ) for ONOO - through a novel and universally applicable mechanism: ONOO - -mediated deprotection of α-keto caged fluorophores. Among them, Rhod-ONOO - can selectively accumulate and react in mitochondria, one of the main sources of ONOO - , with a substantial lower nanomolar sensitivity of 43 nM. The superior selectivity and sensitivity of two probes enable real-time imaging of peroxynitrite generation in lipopolysaccharide-stimulated live cells, with a remarkable difference from cells doped with other interfering reactive oxygen species, in either one- or two-photon imaging modes. More importantly, we elucidated the drug-induced hepatotoxicity pathway with Rhod-ONOO - and revealed that CYP450/CYP2E1-mediated enzymatic metabolism of acetaminophen leads to ONOO - generation in liver cells. This is the first time to showcase the drug-induced hepatotoxicity pathways by use of a small-molecule fluorescent probe. We hence conclude that fluorescent probes can engender a deeper understanding of reactive species and their pathological revelations. The reaction-based fluorescent probes will be a potentially useful chemical tool to assay drug-induced hepatotoxicity.

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bone, Sharon E.; Dynes, James J.; Cliff, John

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Uranium(IV) adsorption by natural organic matter in anoxic sediments

DOE PAGES

Bone, Sharon E.; Dynes, James J.; Cliff, John; ...

2017-01-09

Uranium is an important carbon-free fuel source and environmental contaminant that accumulates in the tetravalent state, U(IV), in anoxic sediments, such as ore deposits, marine basins, and contaminated aquifers. However, little is known about the speciation of U(IV) in low-temperature geochemical environments, inhibiting the development of a conceptual model of U behavior. Until recently, U(IV) was assumed to exist predominantly as the sparingly soluble mineral uraninite (UO 2+x) in anoxic sediments; however, studies now show that this is not often the case. Yet a model of U(IV) speciation in the absence of mineral formation under field-relevant conditions has not yetmore » been developed. Uranium(IV) speciation controls its reactivity, particularly its susceptibility to oxidative mobilization, impacting its distribution and toxicity. Here we show adsorption to organic carbon and organic carbon-coated clays dominate U(IV) speciation in an organic-rich natural substrate under field-relevant conditions. Whereas previous research assumed that U(IV) speciation is dictated by the mode of reduction (i.e., whether reduction is mediated by microbes or by inorganic reductants), our results demonstrate that mineral formation can be diminished in favor of adsorption, regardless of reduction pathway. Projections of U transport and bioavailability, and thus its threat to human and ecosystem health, must consider U(IV) adsorption to organic matter within the sediment environment.« less

Computational Prediction and Validation of an Expert's Evaluation of Chemical Probes

PubMed Central

Litterman, Nadia K.; Lipinski, Christopher A.; Bunin, Barry A.; Ekins, Sean

2016-01-01

In a decade with over half a billion dollars of investment, more than 300 chemical probes have been identified to have biological activity through NIH funded screening efforts. We have collected the evaluations of an experienced medicinal chemist on the likely chemistry quality of these probes based on a number of criteria including literature related to the probe and potential chemical reactivity. Over 20% of these probes were found to be undesirable. Analysis of the molecular properties of these compounds scored as desirable suggested higher pKa, molecular weight, heavy atom count and rotatable bond number. We were particularly interested whether the human evaluation aspect of medicinal chemistry due diligence could be computationally predicted. We used a process of sequential Bayesian model building and iterative testing as we included additional probes. Following external validation of these methods and comparing different machine learning methods we identified Bayesian models with accuracy comparable to other measures of drug-likeness and filtering rules created to date. PMID:25244007

Adsorption of antimony onto iron oxyhydroxides: adsorption behavior and surface structure.

PubMed

Guo, Xuejun; Wu, Zhijun; He, Mengchang; Meng, Xiaoguang; Jin, Xin; Qiu, Nan; Zhang, Jing

2014-07-15

Antimony is detected in soil and water with elevated concentration due to a variety of industrial applications and mining activities. Though antimony is classified as a pollutant of priority interest by the United States Environmental Protection Agency (USEPA) and Europe Union (EU), very little is known about its environmental behavior and adsorption mechanism. In this study, the adsorption behaviors and surface structure of antimony (III/V) on iron oxides were investigated using batch adsorption techniques, surface complexation modeling (SCM), X-ray photon spectroscopy (XPS) and extended X-ray absorption fine structure spectroscopy (EXAFS). The adsorption isotherms and edges indicated that the affinity of Sb(V) and Sb(III) toward the iron oxides depended on the Sb species, solution pH, and the characteristics of iron oxides. Sb(V) adsorption was favored at acidic pH and decreased dramatically with increasing pH, while Sb(III) adsorption was constant over a broad pH range. When pH is higher than 7, Sb(III) adsorption by goethite and hydrous ferric oxide (HFO) was greater than Sb(V). EXAFS analysis indicated that the majority of Sb(III), either adsorbed onto HFO or co-precipitated by FeCl3, was oxidized into Sb(V) probably due to the involvement of O2 in the long duration of sample preservation. Only one Sb-Fe subshell was filtered in the EXAFS spectra of antimony adsorption onto HFO, with the coordination number of 1.0-1.9 attributed to bidentate mononuclear edge-sharing ((2)E) between Sb and HFO. Copyright © 2014 Elsevier B.V. All rights reserved.

Adsorption of CO and O2 molecules on Li metal adsorbed graphene: Search for graphene based gas sensors

NASA Astrophysics Data System (ADS)

Kaur, Gagandeep; Gupta, Shuchi; Sachdeva, Ritika; Dharamvir, Keya

2018-05-01

Adsorption of small gas molecules (such as CO and O2) on pristine graphene (PG) and Li-adsorbed graphene (PG-Li) have been investigated using first principles methods within density functional theory (DFT). We also notice that PG-Li has a higher chemical reactivity towards the gas molecules as compared to PG and these molecules have higher adsorption energy on this surface. Moreover, the strong interactions between PG-Li and the adsorbed molecules (as compared to PG and gas molecules) induce dramatic changes to the electronic properties of PG adsorbed with Li and make PG-Li a promising candidate as sensing material for CO and O2 gases.

Process Diagnostics and Monitoring Using the Multipole Resonance Probe (MRP)

NASA Astrophysics Data System (ADS)

Harhausen, J.; Awakowicz, P.; Brinkmann, R. P.; Foest, R.; Lapke, M.; Musch, T.; Mussenbrock, T.; Oberrath, J.; Ohl, A.; Rolfes, I.; Schulz, Ch.; Storch, R.; Styrnoll, T.

2011-10-01

In this contribution we present the application of the MRP in an industrial plasma ion assisted deposition (PIAD) chamber (Leybold optics SYRUS-pro). The MRP is a novel plasma diagnostic which is suitable for an industrial environment - which means that the proposed method is robust, calibration free, and economical, and can be used for ideal and reactive plasmas alike. In order to employ the MRP as process diagnostics we mounted the probe on a manipulator to obtain spatially resolved information on the electron density and temperature. As monitoring tool the MRP is installed at a fixed position. Even during the deposition process it provides stable measurement results while other diagnostic methods, e.g. the Langmuir probe, may suffer from dielectric coatings. In this contribution we present the application of the MRP in an industrial plasma ion assisted deposition (PIAD) chamber (Leybold optics SYRUS-pro). The MRP is a novel plasma diagnostic which is suitable for an industrial environment - which means that the proposed method is robust, calibration free, and economical, and can be used for ideal and reactive plasmas alike. In order to employ the MRP as process diagnostics we mounted the probe on a manipulator to obtain spatially resolved information on the electron density and temperature. As monitoring tool the MRP is installed at a fixed position. Even during the deposition process it provides stable measurement results while other diagnostic methods, e.g. the Langmuir probe, may suffer from dielectric coatings. Funded by the German Ministry for Education and Research (BMBF, Fkz. 13N10462).

Reversible adsorption and flushing of arsenic in a shallow, Holocene aquifer of Bangladesh

PubMed Central

Radloff, Kathleen A.; Zheng, Yan; Stute, Martin; Weinman, Beth; Bostick, Benjamin; Mihajlov, Ivan; Bounds, Margaret; Rahman, M. Moshiur; Huq, M. Rezaul; Ahmed, Kazi M.; Schlosser, Peter; van Geen, Alexander

2015-01-01

The spatial heterogeneity of dissolved arsenic (As) concentrations in shallow groundwater of the Bengal Basin has been attributed to transport of As (and reactive carbon) from external sources or to the release of As from within grey sand formations. We explore the latter scenario in this detailed hydrological and geochemical study along a 300 m transect of a shallow aquifer extending from a groundwater recharge area within a sandy channel bar to its discharge into a nearby stream. Within the 10–20 m depth range, groundwater ages along the transect determined by the 3H–3He method increase from <10 yr in the recharge area to a maximum of 40 yr towards the stream. Concentrations of groundwater As within the same grey sands increase from 10 to 100 to ∼500 µg/L along this transect. Evidence of reversible adsorption of As between the groundwater and sediment was obtained from a series of push–pull experiments, traditional batch adsorption experiments, and the accidental flooding of a shallow monitoring well. Assuming reversible adsorption and a distribution coefficient, Kd, of 0.15–1.5 L/kg inferred from these observations, a simple flushing model shows that the increase in As concentrations with depth and groundwater age at this site, and at other sites in the Bengal and Red River Basins, can be attributed to the evolution of the aquifer over 100–1000 years as aquifer sands are gradually flushed of their initial As content. A wide range of As concentrations can thus be maintained in groundwater with increases with depth governed by the history of flushing and local recharge rates, without external inputs of reactive carbon or As from other sources. PMID:28458447

Reversible electrokinetic adsorption barriers for the removal of organochlorine herbicide from spiked soils.

PubMed

Rodrigo, S; Saez, C; Cañizares, P; Rodrigo, M A

2018-06-02

This work aims to describe the removal of clopyralid from clay soils using electrokinetically assisted soil flushing (EKSF) coupled with a permeable reactive barrier (PRB), consisting of beds of Granulated Activated Carbon (GAC). To do this, two strategies have been evaluated on bench-scale electroremediation facilities (175 dm 3 ): electrokinetic adsorption barrier (EKAB) and reversible electrokinetic adsorption barrier (REKAB). Likewise, to clarify the contribution of the different mechanisms to remediation process results are compared to those obtained in a reference test (without applying an electric field) and to results obtained in the EKSF of soils polluted with compounds with different polarity and vapour pressure. Results show that during EKAB and REKAB tests, clopyralid is removed from the soil by adsorption in PRB, electrokinetic transport and, very less decisively, by evaporation. The application of polarity reversion attains a higher retention of clopyralid in the activated carbon-PRB and a better regulation of pH because of the neutralization of H + and OH - generated in the electrolyte wells. After 30 days of operation, the removal of clopyralid by EKAB is 45% while it reaches 57% in the case of REKAB. Copyright © 2018. Published by Elsevier B.V.

Adsorption of Cu(II) to Bacillus subtilis: A pH-dependent EXAFS and thermodynamic modelling study

NASA Astrophysics Data System (ADS)

Moon, Ellen M.; Peacock, Caroline L.

2011-11-01

Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ˜2-7), with adsorption increasing with pH to a maximum at pH ˜6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO 5H n) n-8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1p K basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere tbnd RCOOCu + surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K tbnd RCOOCu + = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.

Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clement, T. Prabhakar; Barnett, Mark O.; Zheng, Chunmiao

DE-FG02-06ER64213: Development of Modeling Methods and Tools for Predicting Coupled Reactive Transport Processes in Porous Media at Multiple Scales Investigators: T. Prabhakar Clement (PD/PI) and Mark O. Barnett (Auburn), Chunmiao Zheng (Univ. of Alabama), and Norman L. Jones (BYU). The objective of this project was to develop scalable modeling approaches for predicting the reactive transport of metal contaminants. We studied two contaminants, a radioactive cation [U(VI)] and a metal(loid) oxyanion system [As(III/V)], and investigated their interactions with two types of subsurface materials, iron and manganese oxyhydroxides. We also developed modeling methods for describing the experimental results. Overall, the project supportedmore » 25 researchers at three universities. Produced 15 journal articles, 3 book chapters, 6 PhD dissertations and 6 MS theses. Three key journal articles are: 1) Jeppu et al., A scalable surface complexation modeling framework for predicting arsenate adsorption on goethite-coated sands, Environ. Eng. Sci., 27(2): 147-158, 2010. 2) Loganathan et al., Scaling of adsorption reactions: U(VI) experiments and modeling, Applied Geochemistry, 24 (11), 2051-2060, 2009. 3) Phillippi, et al., Theoretical solid/solution ratio effects on adsorption and transport: uranium (VI) and carbonate, Soil Sci. Soci. of America, 71:329-335, 2007« less

Reactive wetting properties of TiO2 nanoparticles predicted by ab initio molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Brandt, Erik G.; Agosta, Lorenzo; Lyubartsev, Alexander P.

2016-07-01

Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity.Small-sized wet TiO2 nanoparticles have been investigated by ab initio molecular dynamics simulations. Chemical and physical adsorption of water on the TiO2-water interface was studied as a function of water content, ranging from dry nanoparticles to wet nanoparticles with monolayer coverage of water. The surface reactivity was shown to be a concave function of water content and driven by surface defects. The local coordination number at the defect was identified as the key factor to decide whether water adsorption proceeds through dissociation or physisorption on the surface. A consistent picture of TiO2 nanoparticle wetting at the microscopic level emerges, which corroborates existing experimental data and gives further insight into the molecular mechanisms behind nanoparticle wetting. These calculations will facilitate the engineering of metal oxide nanoparticles with a controlled catalytic water activity. Electronic supplementary information (ESI) available: Simulation data on equilibration of energies and structures (root-mean-square-deviations and

Far Western: probing membranes.

PubMed

Einarson, Margret B; Pugacheva, Elena N; Orlinick, Jason R

2007-08-01

INTRODUCTIONThe far-Western technique described in this protocol is fundamentally similar to Western blotting. In Western blots, an antibody is used to detect a query protein on a membrane. In contrast, in a far-Western blot (also known as an overlay assay) the antibody is replaced by a recombinant GST fusion protein (produced and purified from bacteria), and the assay detects the interaction of this protein with target proteins on a membrane. The membranes are washed and blocked, incubated with probe protein, washed again, and subjected to autoradiography. The GST fusion (probe) proteins are often labeled with (32)P; alternatively, the membrane can be probed with unlabeled GST fusion protein, followed by detection using commercially available GST antibodies. The nonradioactive approach is substantially more expensive (due to the purchase of antibody and detection reagents) than using radioactively labeled proteins. In addition, care must be taken to control for nonspecific interactions with GST alone and a signal resulting from antibody cross-reactivity. In some instances, proteins on the membrane are not able to interact after transfer. This may be due to improper folding, particularly in the case of proteins expressed from a phage expression library. This protocol describes a way to overcome this by washing the membrane in denaturation buffer, which is then serially diluted to permit slow renaturation of the proteins.

A coumarin-based two-photon probe for hydrogen peroxide.

PubMed

Zhang, Kai-Ming; Dou, Wei; Li, Peng-Xuan; Shen, Rong; Ru, Jia-Xi; Liu, Wei; Cui, Yu-Mei; Chen, Chun-Yang; Liu, Wei-Sheng; Bai, De-Cheng

2015-02-15

A new fluorescence probe was developed for hydrogen peroxide (H2O2) detection based on donor-excited photo induced electron transfer (D-PET) mechanism, together with the benzil as a quenching and recognizing moiety. The benzil could convert to benzoic anhydride via a Baeyer-Villiger type reaction in the presence of H2O2, followed by hydrolysis of benzoicanhydride to give benzoic acid, and the fluorophore released. The probe was synthesized by a 6-step procedure starting from 4-(diethylamino)salicylaldehyde. A density functional theory (DFT) calculation was performed to demonstrate that the benzil was a fluorescence quencher. The probe was evaluated in both one-photon and two-photon mode, and it exhibited high selectivity toward H2O2 over other reactive oxygen species and high sensitivity with a detection limit of 0.09 μM. Furthermore, the probe was successfully applied to cell imaging of intracellular H2O2 levels with one-photon microscopy and two-photon microscopy. The superior properties of the probe made it of great potential use in more chemical and biological researches. Copyright © 2014 Elsevier B.V. All rights reserved.

Understanding structure, metal distribution, and water adsorption in mixed-metal MOF-74

DOE PAGES

Howe, Joshua D.; Morelock, Cody R.; Jiao, Yang; ...

2016-11-30

We present a joint computational and experimental study of Mg–Ni-MOF-74 and Mg–Cd-MOF-74 to gain insight into the mixing of metals and understand how metal mixing affects the structure of the undercoordinated open-metal sites. Our calculations predict that metal mixing is energetically preferred in these materials. Recent experimental work has demonstrated that Mg–Ni-MOF-74 shows a much greater surface area retention in the presence of water than Mg-MOF-74. To probe this effect, we study H 2O adsorption in Mg–Ni-MOF-74, finding that the adsorption energetics and electronic structure do not change significantly at the metal sites when compared to Mg-MOF-74 and Ni-MOF-74, respectively.more » Lastly, we conclude that the increased stability of Mg–Ni-MOF-74 is a result of a M–O bond length distortion in mixed-metal MOF-74, consistent with recent work on the stability of MOF-74 under water exposure.« less

Horizontal and vertical structure of reactive bromine events probed by bromine monoxide MAX-DOAS

NASA Astrophysics Data System (ADS)

Simpson, William R.; Peterson, Peter K.; Frieß, Udo; Sihler, Holger; Lampel, Johannes; Platt, Ulrich; Moore, Chris; Pratt, Kerri; Shepson, Paul; Halfacre, John; Nghiem, Son V.

2017-08-01

Heterogeneous photochemistry converts bromide (Br-) to reactive bromine species (Br atoms and bromine monoxide, BrO) that dominate Arctic springtime chemistry. This phenomenon has many impacts such as boundary-layer ozone depletion, mercury oxidation and deposition, and modification of the fate of hydrocarbon species. To study environmental controls on reactive bromine events, the BRomine, Ozone, and Mercury EXperiment (BROMEX) was carried out from early March to mid-April 2012 near Barrow (Utqiaġvik), Alaska. We measured horizontal and vertical gradients in BrO with multiple-axis differential optical absorption spectroscopy (MAX-DOAS) instrumentation at three sites, two mobile and one fixed. During the campaign, a large crack in the sea ice (an open lead) formed pushing one instrument package ˜ 250 km downwind from Barrow (Utqiaġvik). Convection associated with the open lead converted the BrO vertical structure from a surface-based event to a lofted event downwind of the lead influence. The column abundance of BrO downwind of the re-freezing lead was comparable to upwind amounts, indicating direct reactions on frost flowers or open seawater was not a major reactive bromine source. When these three sites were separated by ˜ 30 km length scales of unbroken sea ice, the BrO amount and vertical distributions were highly correlated for most of the time, indicating the horizontal length scales of BrO events were typically larger than ˜ 30 km in the absence of sea ice features. Although BrO amount and vertical distribution were similar between sites most of the time, rapid changes in BrO with edges significantly smaller than this ˜ 30 km length scale episodically transported between the sites, indicating BrO events were large but with sharp edge contrasts. BrO was often found in shallow layers that recycled reactive bromine via heterogeneous reactions on snowpack. Episodically, these surface-based events propagated aloft when aerosol extinction was higher (> 0.1 km

Adsorption of calcitonin to glass.

PubMed

Law, S L; Shih, C L

1999-02-01

Surface adsorption of calcitonin on soda lime silica glass was investigated. An attempt was also made to examine the effect of additives on the inhibition of calcitonin adsorption. Results showed that the adsorption isotherms were of the Langmuir and Freundlich type, depending on pH. Less adsorption was found for calcitonin at pH 4.3. The addition of nonionic surfactants such as Pluronic F68 and Tween 80 to the calcitonin solutions demonstrated inhibition of absorption and reduction of adsorption rate. The addition of chlorobutanol also showed the effect of minimizing adsorption.

The application of textile sludge adsorbents for the removal of Reactive Red 2 dye.

PubMed

Sonai, Gabriela G; de Souza, Selene M A Guelli U; de Oliveira, Débora; de Souza, Antônio Augusto U

2016-03-01

Sludge from the textile industry was used as a low-cost adsorbent to remove the dye Reactive Red 2 from an aqueous solution. Adsorbents were prepared through the thermal and chemical treatment of sludge originating from physical-chemical (PC) and biological (BIO) effluent treatment processes. The adsorbent characterization was carried out through physical-chemical analysis, X-ray fluorescence (XRF) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, pHPZC determination, Boehm titration method, Brunauer-Emmett-Teller (BET) surface area analysis and scanning electron microscopy (SEM). Batch kinetic experiments and adsorption isotherm modeling were conducted under different pH and temperature conditions. The results for the kinetic studies indicate that the adsorption processes associated with these systems can be described by a pseudo-second-order model and for the equilibrium data the Langmuir model provided the best fit. The adsorption was strongly dependent on the pH but not on the temperature within the ranges studied. The maxima adsorption capacities were 159.3 mg g(-1) for the BIO adsorbent and 213.9 mg g(-1) for PC adsorbent at pH of 2 and 25 °C. Copyright © 2015 Elsevier Ltd. All rights reserved.

Scaling Relations for Acidity and Reactivity of Zeolites

PubMed Central

2017-01-01

Zeolites are widely applied as solid acid catalysts in various technological processes. In this work we have computationally investigated how catalytic reactivity scales with acidity for a range of zeolites with different topologies and chemical compositions. We found that straightforward correlations are limited to zeolites with the same topology. The adsorption energies of bases such as carbon monoxide (CO), acetonitrile (CH3CN), ammonia (NH3), trimethylamine (N(CH3)3), and pyridine (C5H5N) give the same trend of acid strength for FAU zeolites with varying composition. Crystal orbital Hamilton populations (COHP) analysis provides a detailed molecular orbital picture of adsorbed base molecules on the Brønsted acid sites (BAS). Bonding is dominated by strong σ donation from guest molecules to the BAS for the adsorbed CO and CH3CN complexes. An electronic descriptor of acid strength is constructed based on the bond order calculations, which is an intrinsic parameter rather than adsorption energy that contains additional contributions due to secondary effects such as van der Waals interactions with the zeolite walls. The bond order parameter derived for the CH3CN adsorption complex represents a useful descriptor for the intrinsic acid strength of FAU zeolites. For FAU zeolites the activation energy for the conversion of π-adsorbed isobutene into alkoxy species correlates well with the acid strength determined by the NH3 adsorption energies. Other zeolites such as MFI and CHA do not follow the scaling relations obtained for FAU; we ascribe this to the different van der Waals interactions and steric effects induced by zeolite framework topology. PMID:29142616

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

PubMed

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

2013-10-01

Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane. Copyright © 2013 Elsevier Ltd. All rights reserved.

The Reactivity and Structure of Size Selected VxO y Clusters on a TiO2 (110)-(1 X 1) Surface of Variable Oxidation State

NASA Astrophysics Data System (ADS)

Neilson, Hunter L.

The Reactivity and Structure of Size Selected VxOy Clusters on a TiO2 (110) Surface of Variable Oxidation State by Hunter L Neilson The selective oxidative dehydrogenation of methanol by vanadium oxide/TiO2 model systems has received a great deal of interest in the surface science community. Previous studies using temperature programmed desorption and reaction (TPD/R) to probe the oxidation of methanol to formaldehyde by vanadia/TiO2 model catalysts have shown that the activity of these systems vary considerably based on the way in which the model system is prepared with formaldehyde desorption temperatures observed anywhere from room temperature to 660 K. The principle reason for this variation is that the preparation of sub-monolayer films of vanadia on TiO2 produces clusters with a multitude of VxOy structures and a mixture of vanadium oxidation states. As a result the stoichiometry of the active vanadium oxide catalyst as well as the oxidation state of vanadium in the active catalyst remain unknown. To better understand this system, our group has probed the reactivity and structure of size-selected Vx, VOy and VxOy clusters on a reduced TiO2 (110) support in ultra-high vacuum (UHV) via TPD/R and scanning tunneling microscopy (STM). Ex situ preparation of these clusters in the gas phase prior to deposition has allowed us to systematically vary the stoichiometry of the vanadia clusters; a layer of control not available via the usual routes to vanadium oxide. The most active catalysts are shown to have (VO3)n stoichiometry in agreement with the theoretical models of the Metiu group. We have shown that both the activity and selectivity of V2O6 and V3O9 cluster catalysts depend sensitively on the oxidation state of the TiO2 (110) support. For example, V2O6 on a reduced surface is selective for the oxidation of methanol to formaldehyde while the selectivity shifts to favor methyl formate as the surface becomes increasingly oxidized. STM studies show that the

Probing the (110)-Oriented plane of rutile ZnF2: A DFT investigation

NASA Astrophysics Data System (ADS)

Tamijani, Ali Abbaspour; Ebrahimiaqda, Elham

2017-12-01

For many years, rutile-like crystals have given rise to pronounced enthusiasm amongst mineralogists. In this context, rutile-type ZnF2 has found numerous applications across a variety of disciplines, ranging from material sciences to optoelectronics. Surprisingly, very limited literature is concerned with the molecular adsorption on ZnF2 surfaces and related energetics. Additionally, surface probing with small particles is a well-entrenched technique to analyze the interfacial properties. In this regard, small organic species are valuable picks. In the present work, we have employed electronic structure calculations to simulate the adsorption of methane, chloroform, pyrrole, benzene, naphthalene, anthracene, tetracene and pentacene at the (110) plane of rutile ZnF2. Dispersion-corrected DFT method was chosen to predict the binding energies and structures of molecule-adsorbed surfaces. Interestingly, a linear proportionality relationship was found between the binding energies of aromatic adsorbates and their respective molecular lengths. By applying this relationship, we were able to predict the adsorption energy of pentacene on ZnF2 to within 2% of our DFT-based result.

Reduction of non-specific adsorption of drugs to plastic containers used in bioassays or analyses.

PubMed

Fukazawa, Tominaga; Yamazaki, Yuri; Miyamoto, Yohei

2010-01-01

Non-specific adsorption (NSA) of drugs to plastic or glass containers used in clinical use is well known, but methods for reducing NSA have been rarely reported. We assessed the NSA to various containers and then investigated methods to reduce NSA. Probe drugs (methotrexate, warfarin, chloroquine, propranolol, verapamil, digoxin and paclitaxel) dissolved in water were incubated in conventional or low-adsorption containers for 4h at 4 degrees C and the NSA was determined by HPLC. They were also dissolved in aqueous methanol or acetonitrile and the NSA to a conventional polypropylene microplate was determined. Finally, tissue culture microplates were coated with silane coupling agents and the effects of the coatings were evaluated. Hydrophobic drugs (paclitaxel, verapamil and digoxin) were highly adsorbed to conventional plastic microplates, but in addition to hydrophobic drugs, positively charged drugs were well adsorbed to the tissue culture microplate. Low-adsorption microplates could reduce NSA below 15%, but positively charged or neutral hydrophobic drugs showed relatively higher adsorption. Acetonitrile showed stronger NSA inhibition than that of methanol, but the peak shapes of methotrexate and chloroquine were broadened and split. Among the silane coupling agents, GPTMS suppressed the NSA below 10%. Also, AATMS resembled the NSA pattern of GPTMS, but it increased the adsorption of methotrexate to 29%. On conventional plastic microplates, NSA is mainly driven by hydrophobic interactions, but on tissue culture microplates and low-adsorption microplates, in addition to hydrophobic interactions, ionic interactions play a role in the NSA. Therefore, to reduce the NSA to plastic containers, both hydrophobic and ionic interactions should be reduced using amphiphilic organic solvents or neutral and hydrophilic coatings. 2010 Elsevier Inc. All rights reserved.

Adsorption dynamics of CVD graphene investigated by a contactless microwave method

NASA Astrophysics Data System (ADS)

Black, N. C. G.; Rungger, I.; Li, B.; Maier, S. A.; Cohen, L. F.; Gallop, J. C.; Hao, L.

2018-07-01

We use a contactless microwave dielectric resonator gas sensing platform to study the adsorption dynamics of NO2 gas present in air onto a graphene surface. The use of microwaves removes the need for metal contacts that would otherwise be necessary for traditional conductivity measurements, and therefore allows non-invasive determination of NO2 concentrations to sub parts per million. As a result, gas‑metal interactions and localised graphene doping in the vicinity of metal contacts are eliminated, with the advantage that only graphene‑gas adsorbate interactions are responsible for the measured signal. We show that the sensor response for all considered concentrations can be described using a surface coverage dependent Langmuir model. We demonstrate that the possible variation of the NO2 binding energy, which is frequently considered as the main parameter, plays only a secondary role compared to the rising adsorption energy barrier with increasing NO2 coverage. The continuous distribution of the properties of the graphene adsorption sites used in the theoretical model is supported by our Kelvin probe and Raman surface analysis. Our results demonstrate that the non-invasive microwave method is a promising alternative platform for gas sensing. Moreover it provides valuable insights towards the understanding of the microscopic processes occurring in graphene based gas sensors, which is a key factor in the realization of reproducible and optimized device properties.

ReaxFF Grand Canonical Monte Carlo simulation of adsorption and dissociation of oxygen on platinum (111)

NASA Astrophysics Data System (ADS)

Valentini, Paolo; Schwartzentruber, Thomas E.; Cozmuta, Ioana

2011-12-01

Atomic-level Grand Canonical Monte Carlo (GCMC) simulations equipped with a reactive force field (ReaxFF) are used to study atomic oxygen adsorption on a Pt(111) surface. The off-lattice GCMC calculations presented here rely solely on the interatomic potential and do not necessitate the pre-computation of surface adlayer structures and their interpolation. As such, they provide a predictive description of adsorbate phases. In this study, validation is obtained with experimental evidence (steric heats of adsorption and isotherms) as well as DFT-based state diagrams available in the literature. The ReaxFF computed steric heats of adsorption agree well with experimental data, and this study clearly shows that indirect dissociative adsorption of O2 on Pt(111) is an activated process at non-zero coverages, with an activation energy that monotonically increases with coverage. At a coverage of 0.25 ML, a highly ordered p(2 × 2) adlayer is found, in agreement with several low-energy electron diffraction observations. Isotherms obtained from the GCMC simulations compare qualitatively and quantitatively well with previous DFT-based state diagrams, but are in disagreement with the experimental data sets available. ReaxFF GCMC simulations at very high coverages show that O atoms prefer to bind in fcc hollow sites, at least up to 0.8 ML considered in the present work. At moderate coverages, little to no disorder appears in the Pt lattice. At high coverages, some Pt atoms markedly protrude out of the surface plane. This observation is in qualitative agreement with recent STM images of an oxygen covered Pt surface. The use of the GCMC technique based on a transferable potential is particularly valuable to produce more realistic systems (adsorbent and adsorbate) to be used in subsequent dynamical simulations (Molecular Dynamics) to address recombination reactions (via either Eley-Rideal or Langmuir-Hinshelwood mechanisms) on variously covered surfaces. By using GCMC and Molecular

On the Henry constant and isosteric heat at zero loading in gas phase adsorption.

PubMed

Do, D D; Nicholson, D; Do, H D

2008-08-01

The Henry constant and the isosteric heat of adsorption at zero loading are commonly used as indicators of the strength of the affinity of an adsorbate for a solid adsorbent. It is assumed that (i) they are observable in practice, (ii) the Van Hoff's plot of the logarithm of the Henry constant versus the inverse of temperature is always linear and the slope is equal to the heat of adsorption, and (iii) the isosteric heat of adsorption at zero loading is either constant or weakly dependent on temperature. We show in this paper that none of these three points is necessarily correct, first because these variables might not be observable since they are outside the range of measurability; second that the linearity of the Van Hoff plot breaks down at very high temperature, and third that the isosteric heat versus loading is a strong function of temperature. We demonstrate these points using Monte Carlo integration and Monte Carlo simulation of adsorption of various gases on a graphite surface. Another issue concerning the Henry constant is related to the way the adsorption excess is defined. The most commonly used equation is the one that assumes that the void volume is the volume extended all the way to a boundary passing through the centres of the outermost solid atoms. With this definition the Henry constant can become negative at high temperatures. Although adsorption at these temperatures may not be practical because of the very low value of the Henry constant, it is more useful to define the Henry constant in such a way that it is always positive at all temperatures. Here we propose the use of the accessible volume; the volume probed by the adsorbate when it is in nonpositive regions of the potential, to calculate the Henry constant.

Density functional theory study on the interactions of l-cysteine with graphene: adsorption stability and magnetism

NASA Astrophysics Data System (ADS)

Luo, Huijuan; Li, Hejun; Fu, Qiangang; Chu, Yanhui; Cao, Xiaoyu; Sun, Can; Yuan, Xiaoyan; Liu, Lei

2013-12-01

Understanding the interactions between graphene and biomolecules is of fundamental relevance to the area of nanobiotechnology. Herein, we take l-cysteine as the probe biomolecule and investigate its adsorption on pristine graphene and B-, N-, Al-, Ni-, Ga-, Pd-doped graphene using density functional theory calculations. Three kinds of upright adsorption configurations, via unprotonated functional groups (-SH, -NH2, -COOH), are considered. The calculations reveal pristine graphene physically adsorbs l-cysteine. N-doped graphene shows physisorption towards the S-end and N-end l-cysteine, and chemisorption towards the O-end radical. Strong chemisorption, with site-specific preference, occurs on Al-, Ni-, Ga- and Pd-doped graphene, accompanied by severe structural changes. Spin polarization with an unusual mirror symmetry on Ni- and Pd-doped graphene is induced by chemisorption of unprotonated l-cysteine, except for O-end adsorption on Pd-doped graphene. The magnetization arises mainly from spin polarization of the C 2pz orbital, with a minor magnetism located on Ni or Pd. The influence of van der Waals forces is also evaluated. A thorough analysis of the adsorption stability and magnetism of these systems would be beneficial to facilitate applications in graphene-based biosensing, biomolecule immobilization, magnetic bio-separation and other fields in bionanotechnology.

Characterization and evaluation of the novel agarose-nickel composite matrix for possible use in expanded bed adsorption of bio-products.

PubMed

Rezvani, Azita; Jahanshahi, Mohsen; Najafpour, Ghasem D

2014-02-28

Agarose-nickel (Ag-Ni) composite matrix was evaluated for its use in expanded bed adsorption (EBA). Bovine serum albumin (BSA) and lysozyme were used as model proteins in batch and column adsorption studies. Accordingly, Reactive Green 19 (RG19) dye-ligand was covalently immobilized onto the support matrix to prepare affinity adsorbent for protein adsorption. Results were then compared with data obtained from Streamline commercial matrix. In batch experiments RG19 derivatives of Ag-Ni (RG19-Ag-Ni) exhibited high adsorption rate; and also a higher binding capacity of BSA (31.4mg/ml adsorbent) was observed for Ag-Ni compared to the commercial adsorbent. More than 70% of the adsorption capacity was achieved within 30min which is a reasonable contact time for EBA operations. The equilibrium adsorption data well agreed with Langmuir isotherm model. The expanded bed adsorption studies showed a reasonable breakthrough behavior at high flow rates and a higher dynamic binding capacity (DBC) was obtained for novel matrix in compare to streamline at the same fluid velocity. DBC at 10% breakthrough reached 66% of the saturated adsorption capacity at the high flow velocity of 450cm/h which indicates the favorable column efficiency. Additionally, two different Ag-Ni size fractions (75-150 and 150-300μm) were examined to investigate the expanded bed performance dependency on the adsorbent particle size with respect to the hydrodynamic stability and adsorption properties using lysozyme as model protein. Interestingly, the small ones showed less axial dispersion coefficient (<1.0×10(-5)m(2)/s) which resulted in higher bed stability in high fluid viscosities. Overall, the adsorption experiments results demonstrated that small size fraction of Ag-Ni matrices acts more effectively for expanded bed adsorption of bio-molecules. Copyright © 2014 Elsevier B.V. All rights reserved.

Spectral Induced Polarization approaches to characterize reactive transport parameters and processes

NASA Astrophysics Data System (ADS)

Schmutz, M.; Franceschi, M.; Revil, A.; Peruzzo, L.; Maury, T.; Vaudelet, P.; Ghorbani, A.; Hubbard, S. S.

2017-12-01

For almost a decade, geophysical methods have explored the potential for characterization of reactive transport parameters and processes relevant to hydrogeology, contaminant remediation, and oil and gas applications. Spectral Induced Polarization (SIP) methods show particular promise in this endeavour, given the sensitivity of the SIP signature to geological material electrical double layer properties and the critical role of the electrical double layer on reactive transport processes, such as adsorption. In this presentation, we discuss results from several recent studies that have been performed to quantify the value of SIP parameters for characterizing reactive transport parameters. The advances have been realized through performing experimental studies and interpreting their responses using theoretical and numerical approaches. We describe a series of controlled experimental studies that have been performed to quantify the SIP responses to variations in grain size and specific surface area, pore fluid geochemistry, and other factors. We also model chemical reactions at the interface fluid/matrix linked to part of our experimental data set. For some examples, both geochemical modelling and measurements are integrated into a SIP physico-chemical based model. Our studies indicate both the potential of and the opportunity for using SIP to estimate reactive transport parameters. In case of well sorted granulometry of the samples, we find that the grain size characterization (as well as the permeabililty for some specific examples) value can be estimated using SIP. We show that SIP is sensitive to physico-chemical conditions at the fluid/mineral interface, including the different pore fluid dissolved ions (Na+, Cu2+, Zn2+, Pb2+) due to their different adsorption behavior. We also showed the relevance of our approach to characterize the fluid/matrix interaction for various organic contents (wetting and non-wetting oils). We also discuss early efforts to jointly

Density functional theory and surface reactivity study of bimetallic AgnYm (n+m = 10) clusters

NASA Astrophysics Data System (ADS)

Hussain, Riaz; Hussain, Abdullah Ijaz; Chatha, Shahzad Ali Shahid; Hussain, Riaz; Hanif, Usman; Ayub, Khurshid

2018-06-01

Density functional theory calculations have been performed on pure silver (Agn), yttrium (Ym) and bimetallic silver yttrium clusters AgnYm (n + m = 2-10) for reactivity descriptors in order to realize sites for nucleophilic and electrophilic attack. The reactivity descriptors of the clusters, studied as a function of cluster size and shape, reveal the presence of different type of reactive sites in a cluster. The size and shape of the pure silver, yttrium and bimetallic silver yttrium cluster (n = 2-10) strongly influences the number and position of active sites for an electrophilic and/or nucleophilic attack. The trends of reactivities through reactivity descriptors are confirmed through comparison with experimental data for CO binding with silver clusters. Moreover, the adsorption of CO on bimetallic silver yttrium clusters is also evaluated. The trends of binding energies support the reactivity descriptors values. Doping of pure cluster with the other element also influence the hardness, softness and chemical reactivity of the clusters. The softness increases as we increase the number of silver atoms in the cluster, whereas the hardness decreases. The chemical reactivity increases with silver doping whereas it decreases by increasing yttrium concentration. Silver atoms are nucleophilic in small clusters but changed to electrophilic in large clusters.

Oxalate-curcumin–based probe for micro- and macroimaging of reactive oxygen species in Alzheimer’s disease

PubMed Central

Yang, Jian; Zhang, Xueli; Yang, Jing; Xu, Yungen; Grutzendler, Jaime; Shao, Yihan; Moore, Anna; Ran, Chongzhao

2017-01-01

Alzheimer’s disease (AD) is an irreversible neurodegenerative disorder that has a progression that is closely associated with oxidative stress. It has long been speculated that the reactive oxygen species (ROS) level in AD brains is much higher than that in healthy brains. However, evidence from living beings is scarce. Inspired by the “chemistry of glow stick,” we designed a near-IR fluorescence (NIRF) imaging probe, termed CRANAD-61, for sensing ROS to provide evidence at micro- and macrolevels. In CRANAD-61, an oxalate moiety was utilized to react with ROS and to consequentially produce wavelength shifting. Our in vitro data showed that CRANAD-61 was highly sensitive and rapidly responsive to various ROS. On reacting with ROS, its excitation and emission wavelengths significantly shifted to short wavelengths, and this shifting could be harnessed for dual-color two-photon imaging and transformative NIRF imaging. In this report, we showed that CRANAD-61 could be used to identify “active” amyloid beta (Aβ) plaques and cerebral amyloid angiopathy (CAA) surrounded by high ROS levels with two-photon imaging (microlevel) and to provide relative total ROS concentrations in AD brains via whole-brain NIRF imaging (macrolevel). Lastly, we showed that age-related increases in ROS levels in AD brains could be monitored with our NIRF imaging method. We believe that our imaging with CRANAD-61 could provide evidence of ROS at micro- and macrolevels and could be used for monitoring ROS changes under various AD pathological conditions and during drug treatment. PMID:29109280

Application of low energy ion blocking for adsorption site determination of Na Atoms on a Cu(111) surface

NASA Astrophysics Data System (ADS)

Zhang, R.; Makarenko, B.; Bahrim, B.; Rabalais, J. W.

2010-07-01

Ion blocking in the low keV energy range is demonstrated to be a sensitive method for probing surface adsorption sites by means of the technique of time-of-flight scattering and recoiling spectroscopy (TOF-SARS). Adsorbed atoms can block the nearly isotropic backscattering of primary ions from surface atoms in the outmost layers of a crystal. The relative adsorption site position can be derived unambiguously by simple geometrical constructs between the adsorbed atom site and the surface atom sites. Classical ion trajectory simulations using the scattering and recoiling imaging code (SARIC) and molecular dynamics (MD) simulations provide the detailed ion trajectories. Herein we present a quantitative analysis of the blocking effects produced by sub-monolayer Na adsorbed on a Cu(111) surface at room temperature. The results show that the Na adsorption site preferences are different at different Na coverages. At a coverage θ = 0.25 monolayer, Na atoms preferentially populate the fcc threefold surface sites with a height of 2.7 ± 0.1 Å above the 1st layer Cu atoms. At a lower coverage of θ = 0.10 monolayer, there is no adsorption site preference for the Na atoms on the Cu(111) surface.

Oxidative potential of logwood and pellet burning particles assessed by a novel profluorescent nitroxide probe.

PubMed

Miljevic, B; Heringa, M F; Keller, A; Meyer, N K; Good, J; Lauber, A; Decarlo, P F; Fairfull-Smith, K E; Nussbaumer, T; Burtscher, H; Prevot, A S H; Baltensperger, U; Bottle, S E; Ristovski, Z D

2010-09-01

This study reports the potential toxicological impact of particles produced during biomass combustion by an automatic pellet boiler and a traditional logwood stove under various combustion conditions using a novel profluorescent nitroxide probe, BPEAnit. This probe is weakly fluorescent but yields strong fluorescence emission upon radical trapping or redox activity. Samples were collected by bubbling aerosol through an impinger containing BPEAnit solution, followed by fluorescence measurement. The fluorescence of BPEAnit was measured for particles produced during various combustion phases: at the beginning of burning (cold start), stable combustion after refilling with the fuel (warm start), and poor burning conditions. For particles produced by the logwood stove under cold-start conditions, significantly higher amounts of reactive species per unit of particulate mass were observed compared to emissions produced during a warm start. In addition, sampling of logwood burning emissions after passing through a thermodenuder at 250 degrees C resulted in an 80-100% reduction of the fluorescence signal of the BPEAnit probe, indicating that the majority of reactive species were semivolatile. Moreover, the amount of reactive species showed a strong correlation with the amount of particulate organic material. This indicates the importance of semivolatile organics in particle-related toxicity. Particle emissions from the pellet boiler, although of similar mass concentration, were not observed to lead to an increase in fluorescence signal during any of the combustion phases.

Arsenic Adsorption Equilibrium Concentration and Adsorption Rate of Activated Carbon Coated with Ferric-Aluminum Hydroxides

NASA Astrophysics Data System (ADS)

Zhang, M.; Sugita, H.; Oguma, T.; Hara, J.; Takahashi, S.

2015-12-01

In some areas of developing countries, ground or well water contaminated with arsenic has been reluctantly used as drinking water. It is highly desirable that effective and inexpensive arsenic removal agents should be developed and provided to reduce the potential health risk. Previous studies demonstrated that activated carbon coated with ferric-aluminum hydroxides (Fe-Al-C) has high adsorptive potential for removal of arsenic. In this study, a series of experiments using Fe-Al-C were carried to discuss adsorption equilibrium time, adsorption equilibrium concentration and adsorption rate of arsenic for Fe-Al-C. Fe-Al-C used in this study was provided by Astec Co., Ltd. Powder reagent of disodium hydrogen arsenate heptahydrate was dissolved into ion-exchanged water. The solution was then further diluted with ion-exchanged water to be 1 and 10 mg/L as arsenic concentration. The pH of the solution was adjusted to be around 7 by adding HCl and/or NaOH. The solution was used as artificial arsenic contaminated water in two types of experiments (arsenic adsorption equilibrium and arsenic adsorption rate tests). The results of the arsenic equilibrium tests were showed that a time period of about 3 days to reach apparent adsorption equilibrium for arsenic. The apparent adsorption equilibrium concentration and adsorbed amount of arsenic on Fe-Al-C adsorbent could be estimated by application of various adsorption isotherms, but the distribution coefficient of arsenic between solid and liquid varies with experimental conditions such as initial concentration of arsenic and addition concentration of adsorbent. An adsorption rate equation that takes into account the reduction in the number of effective adsorption sites on the adsorbent caused by the arsenic adsorption reaction was derived based on the data obtained from the arsenic adsorption rate tests.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

PubMed

Song, Jinsuk; Kim, Mahn Won

2010-03-11

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

Removal of steroid estrogens from wastewater using granular activated carbon: comparison between virgin and reactivated carbon.

PubMed

Rowsell, Victoria Francesca; Pang, Dawn Sok Cheng; Tsafou, Foteini; Voulvoulis, Nikolaos

2009-04-01

This research was set up in response to new European legislation to identify cost-effective treatment for removal of steroid estrogens from effluent. This study aimed to compare estrogen removal of two types of granular activated carbon: virgin (F400) and reactivated (C401) carbon. Rapid, small-scale column tests were conducted with a total bed volume of 24.9 cm3 over three columns, and analysis was carried out using high-performance liquid chromatography. Results demonstrated that C401 performed more efficiently with greater than or equal to 81% estrogen removal in wastewater compared to F400 which produced greater than or equal to 65% estrogen removal. Estrogen removal can be affected by competitive adsorption from natural organic matter present in wastewater. In addition, the physical properties of each carbon had the potential to influence adsorption differently, thus resulting in the observed varied adsorption capability of the two carbons.

Protein Conformational Dynamics Probed by Single-Molecule Electron Transfer

NASA Astrophysics Data System (ADS)

Yang, Haw; Luo, Guobin; Karnchanaphanurach, Pallop; Louie, Tai-Man; Rech, Ivan; Cova, Sergio; Xun, Luying; Xie, X. Sunney

2003-10-01

Electron transfer is used as a probe for angstrom-scale structural changes in single protein molecules. In a flavin reductase, the fluorescence of flavin is quenched by a nearby tyrosine residue by means of photo-induced electron transfer. By probing the fluorescence lifetime of the single flavin on a photon-by-photon basis, we were able to observe the variation of flavin-tyrosine distance over time. We could then determine the potential of mean force between the flavin and the tyrosine, and a correlation analysis revealed conformational fluctuation at multiple time scales spanning from hundreds of microseconds to seconds. This phenomenon suggests the existence of multiple interconverting conformers related to the fluctuating catalytic reactivity.

Organic and inorganic molecules as probes of mineral surfaces (Invited)

NASA Astrophysics Data System (ADS)

Sverjensky, D. A.

2010-12-01

Although the multi-site nature of mineral surfaces is to be expected based on the underlying crystal structure, definitive evidence of the need to use more than one site in modelling proton surface charge or adsorption of a single adsorbate at the mineral-water interface is lacking. Instead, a single-site approach affords a practical way of averaging over all possible crystal planes and sites in a powdered mineral sample. Extensive analysis of published proton surface charge and adsorption of metals on oxide mineral surfaces can be undertaken with a single site density for each mineral based on tritium exchange or estimation from averages of the site densities of likely exposed surfaces. Even in systems with competing metals (e.g. Cu and Pb on hematite), the same site density as used for proton surface charge can be employed depending on the reaction stoichiometry. All of this indicates that protons and metals can bind to a great variety of sites with the same overall site density. However, simple oxyanions such as carbonate, sulfate, selenate, arsenate and arsenite require a much lower site density for a given mineral. For example, on goethite these oxyanions utilize a site density that correlates with the BET surface area of the goethite. In this way, the oxyanions can be thought of as selectively probing the available sites on the mineral. The correlation probably arises because goethites with different BET surface areas have different proportions of singly and multiply-bonded oxygens, and only the singly-bonded oxygens are useful for inner-sphere surface complexation by the ligand exchange mechanism. Small organic molecules behave in a remarkably similar way. For example, adsorption of oxalate on goethite, and aspartate, glutamate, dihydroxyphenylalanine, lysine and arginine on rutile are all consistent with a much smaller site density than those required for metals such as calcium or neodymium. Overall, these results suggest that both inorganic oxyanions and

Influence of LaFeO 3 Surface Termination on Water Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stoerzinger, Kelsey A.; Comes, Ryan; Spurgeon, Steven R.

2017-02-17

The polarity of oxide surfaces can dramatically impact their surface reactivity, in particular with polar molecules such as water. The surface species that result from this interaction change the oxide electronic structure and chemical reactivity in applications such as photoelectrochemistry, but are challenging to probe experimentally with atomic-scale understanding. Here we report a detailed study of the surface chemistry and electronic structure of the perovskite LaFeO3 in humid conditions using ambient pressure X-ray photoelectron spectroscopy. Comparing the two possible terminations of the polar (001)-oriented surface, we find that the LaO surface is more reactive toward water, forming hydroxyl species andmore » adsorbing molecular water at lower relative humidity than its FeO2-terminated counterpart. Our results demonstrate how the termination of a complex oxide can dramatically impact its reactivity, providing insight into the design of catalyst materials.« less

Diketopyrrolopyrrole: brilliant red pigment dye-based fluorescent probes and their applications.

PubMed

Kaur, Matinder; Choi, Dong Hoon

2015-01-07

The development of fluorescent probes for the detection of biologically relevant species is a burgeoning topic in the field of supramolecular chemistry. A number of available dyes such as rhodamine, coumarin, fluorescein, and cyanine have been employed in the design and synthesis of new fluorescent probes. However, diketopyrrolopyrrole (DPP) and its derivatives have a distinguished role in supramolecular chemistry for the design of fluorescent dyes. DPP dyes offer distinctive advantages relative to other organic dyes, including high fluorescence quantum yields and good light and thermal stability. Significant advancements have been made in the development of new fluorescent probes based on DPP in recent years as a result of tireless research efforts by the chemistry scientific community. In this tutorial review, we highlight the recent progress in the development of DPP-based fluorescent probes for the period spanning 2009 to the present time and the applications of these probes to recognition of biologically relevant species including anions, cations, reactive oxygen species, thiols, gases and other miscellaneous applications. This review is targeted toward providing the readers with deeper understanding for the future design of DPP-based fluorogenic probes for chemical and biological applications.

Redox-Responsive Fluorescent Probes with Different Design Strategies.

PubMed

Lou, Zhangrong; Li, Peng; Han, Keli

2015-05-19

In an aerobic organism, reactive oxygen species (ROS) are an inevitable metabolic byproduct. Endogenously produced ROS have a significant role in physiological processes, but excess ROS can cause oxidative stress and can damage tissue. Cells possess elaborate mechanisms to regulate their internal redox status. The intracellular redox homeostasis plays an essential role in maintaining cellular function. However, moderate alterations in redox balance can accompany major transitions in a cell's life cycle. Because of the role of ROS in physiology and in pathology, researchers need new tools to study redox chemistry in biological systems.In recent years, researchers have made remarkable progress in developing new, highly sensitive and selective fluorescent probes that respond to redox changes, and in this Account we highlight related research, primarily from our own group. We present an overview of the design, photophysical properties, and fluorescence transduction mechanisms of reported molecules that probe redox changes. We have designed and synthesized a series of fluorescent probes for redox cycles in biological systems relying on the active center of glutathione peroxidase (GPx). We have also constructed probes based on the oxidation and reduction of hydroquinone and of 2,2,6,6-tetramethylpiperidinooxy (TEMPO). Most of these probes exhibit high sensitivity and good selectivity, absorb in the near-infrared, and respond rapidly. Such probes are useful for confocal fluorescence microscopy, a dynamic imaging technique that could allow researchers to observe biologically important ROS and antioxidants in real time. This technique and these probes provide potentially useful tools for exploring the generation, transport, physiological function, and pathogenic mechanisms of ROS and antioxidants.We also describe features that could improve the properties of redox-responsive fluorescent probes: greater photostability; rapid, dynamic, cyclic and ratiometric responses; and

Automated design of genomic Southern blot probes

PubMed Central

2010-01-01

Background Sothern blotting is a DNA analysis technique that has found widespread application in molecular biology. It has been used for gene discovery and mapping and has diagnostic and forensic applications, including mutation detection in patient samples and DNA fingerprinting in criminal investigations. Southern blotting has been employed as the definitive method for detecting transgene integration, and successful homologous recombination in gene targeting experiments. The technique employs a labeled DNA probe to detect a specific DNA sequence in a complex DNA sample that has been separated by restriction-digest and gel electrophoresis. Critically for the technique to succeed the probe must be unique to the target locus so as not to cross-hybridize to other endogenous DNA within the sample. Investigators routinely employ a manual approach to probe design. A genome browser is used to extract DNA sequence from the locus of interest, which is searched against the target genome using a BLAST-like tool. Ideally a single perfect match is obtained to the target, with little cross-reactivity caused by homologous DNA sequence present in the genome and/or repetitive and low-complexity elements in the candidate probe. This is a labor intensive process often requiring several attempts to find a suitable probe for laboratory testing. Results We have written an informatic pipeline to automatically design genomic Sothern blot probes that specifically attempts to optimize the resultant probe, employing a brute-force strategy of generating many candidate probes of acceptable length in the user-specified design window, searching all against the target genome, then scoring and ranking the candidates by uniqueness and repetitive DNA element content. Using these in silico measures we can automatically design probes that we predict to perform as well, or better, than our previous manual designs, while considerably reducing design time. We went on to experimentally validate a number

Method and apparatus for measuring reactivity of fissile material

DOEpatents

Lee, D.M.; Lindquist, L.O.

1982-09-07

Given are a method and apparatus for measuring nondestructively and noninvasively (i.e., using no internal probing) the burnup, reactivity, or fissile content of any material which emits neutrons and which has fissionable components. The assay is accomplished by altering the return flux of neutrons into the fuel assembly by means of changing the reflecting material. The existing passive neutron emissions in the material being assayed are used as the source of interrogating neutrons. Two measurements of either emitted neutron or emitted gamma-ray count rates are made and are then correlated to either reactivity, burnup, or fissionable content of the material being assayed, thus providing a measurement of either reactivity, burnup, or fissionable content of the material being assayed. Spent fuel which has been freshly discharged from a reactor can be assayed using this method and apparatus. Precisions of 1000 MWd/tU appear to be feasible.

Chemical reactive features of novel amino acids intercalated layered double hydroxides in As(III) and As(V) adsorption.

PubMed

Shen, Liang; Jiang, Xiuli; Chen, Zheng; Fu, Dun; Li, Qingbiao; Ouyang, Tong; Wang, Yuanpeng

2017-06-01

Layered double hydroxides (LDHs) intercalated with amino acids such as methionine (Met) were synthesized as new adsorbents to remediate arsenic-polluted water. This Zn 2 Al-Met-LDHs, identified with the formula of Zn 0.7 Al 0.3 (OH) 2 (Met) 0.3 ·0.32H 2 O, has good thermal stability. Adsorption experiments with Zn 2 Al-Met-LDHs showed that the residual arsenic in solution could be reduced below the regulation limit, and this adsorption process fitted Langmuir isotherm and the pseudo-second-order kinetics well. A remarkably high removal efficiency and the maximum adsorption capacity for As(III) were achieved, 96.7% and 94.1 mg/g, respectively, at 298 K. The desorption efficiency of As(III) from the arsenic-saturated Zn 2 Al-Met-LDHs (<8.7%), far less than that of As(V), promises a specific and reliable uptake of As(III) in sorts of solutions. More importantly, a complete and in-depth spectra analysis through FTIR, XPS and NMR was conducted to explain the excellent performance of Zn 2 Al-Met-LDHs in arsenic removal. Herein, two special chemical reactions were proposed as the dominant mechanisms, i.e., hydrogen bonding between the carboxyl group of the host Met and the hydroxyl group of As(III) or As(V), and the formation of a chelate ring between the guest As(III) and the S, N bidentate ligands of the intercalated Met in the LDHs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Plane wave packet formulation of atom-plus-diatom quantum reactive scattering.

PubMed

Althorpe, Stuart C

2004-07-15

We recently interpreted several reactive scattering experiments using a plane wave packet (PWP) formulation of quantum scattering theory [see, e.g., S. C. Althorpe, F. Fernandez-Alonso, B. D. Bean, J. D. Ayers, A. E. Pomerantz, R. N. Zare, and E. Wrede, Nature (London) 416, 67 (2002)]. This paper presents the first derivation of this formulation for atom-plus-diatom reactive scattering, and explains its relation to conventional time-independent reactive scattering. We generalize recent results for spherical-particle scattering [S. C. Althorpe, Phys. Rev. A 69, 042702 (2004)] to atom-rigid-rotor scattering in the space-fixed frame, atom-rigid-rotor scattering in the body-fixed frame, and finally A+BC rearrangement scattering. The reactive scattering is initiated by a plane wave packet, describing the A+BC reagents in center-of-mass scattering coordinates, and is detected by projecting onto a series of AC+B (or AB+C) plane wave "probe" packets. The plane wave packets are localized at the closest distance from the scattering center at which the interaction potential can be neglected. The time evolution of the initial plane wave packet provides a clear visualization of the scattering into space of the reaction products. The projection onto the probe packets yields the time-independent, state-to-state scattering amplitude, and hence the differential cross section. We explain how best to implement the PWP approach in a numerical computation, and illustrate this with a detailed application to the H+D2 reaction. (c) 2004 American Institute of Physics

Universality of crossover scaling for the adsorption transition of lattice polymers

NASA Astrophysics Data System (ADS)

Bradly, C. J.; Owczarek, A. L.; Prellberg, T.

2018-02-01

Recently, it has been proposed that the adsorption transition for a single polymer in dilute solution, modeled by lattice walks in three dimensions, is not universal with respect to intermonomer interactions. Moreover, it has been conjectured that key critical exponents ϕ , measuring the growth of the contacts with the surface at the adsorption point, and 1 /δ , which measures the finite-size shift of the critical temperature, are not the same. However, applying standard scaling arguments the two key critical exponents should rather be identical, hence pointing to a potential breakdown of these standard scaling arguments. Both of these conjectures are in contrast to the well-studied situation in two dimensions, where there are exact results from conformal field theory: these exponents are both accepted to be 1 /2 and universal. We use the flatPERM algorithm to simulate self-avoiding walks and trails on the hexagonal, square, and simple cubic lattices up to length 1024 to investigate these claims. Walks can be seen as a repulsive limit of intermonomer interaction for trails, allowing us to probe the universality of adsorption. For each lattice model we analyze several thermodynamic properties to produce different methods of estimating the critical temperature and the key exponents. We test our methodology on the two-dimensional cases, and the resulting spread in values for ϕ and 1 /δ indicates that there is a systematic error which can far exceed the statistical error usually reported. We further suggest a methodology for consistent estimation of the key adsorption exponents which gives ϕ =1 /δ =0.484 (4 ) in three dimensions. Hence, we conclude that in three dimensions these critical exponents indeed differ from the mean-field value of 1 /2 , as had previously been calculated, but cannot find evidence that they differ from each other. Importantly, we also find no substantive evidence of any nonuniversality in the polymer adsorption transition.

Flexible deep brain neural probes based on a parylene tube structure

NASA Astrophysics Data System (ADS)

Zhao, Zhiguo; Kim, Eric; Luo, Hao; Zhang, Jinsheng; Xu, Yong

2018-01-01

Most microfabricated neural probes have limited shank length, which prevents them from reaching many deep brain structures. This paper reports deep brain neural probes with ultra-long penetrating shanks based on a simple but novel parylene tube structure. The mechanical strength of the parylene tube shank is temporarily enhanced during implantation by inserting a metal wire. The metal wire can be removed after implantation, making the implanted probe very flexible and thus minimizing the stress caused by micromotions of brain tissues. Optogenetic stimulation and chemical delivery capabilities can be potentially integrated by taking advantage of the tube structure. Single-shank prototypes with a shank length of 18.2 mm have been developed. The microfabrication process comprises of deep reactive ion etching (DRIE) of silicon, parylene conformal coating/refilling, and XeF2 isotropic silicon etching. In addition to bench-top insertion characterization, the functionality of developed probes has been preliminarily demonstrated by implanting into the amygdala of a rat and recording neural signals.

Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: A promising heavy metal sensing material in farmland

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2017-03-01

Density functional theory calculations are carried out to study the adsorption of mercury and arsenic on Pdn (n = 1-6) supported on pyridine-like nitrogen doped graphene (PNG). Owing to the promising sensitivity in trace amounts of atoms or molecules, PNG can be acted as micro-sensor for sensing heavy metals in agriculture soils. Through the analyses of structural and electronic properties of pristine PNG and Pd atom decorated PNG, we find that the most favorable adsorption site for Pd atom is the vacancy site. The analyses of structural and electronic properties reveal that the Pd atom or clusters can enhance the reactivity for Hg and AsH3 adsorption on PNG. The adsorption ability of Hg on Pdn decorated PNG is found to be related to the d-band center (εd) of the Pdn, in which the closer εd of Pdn to the Fermi level, the higher adsorption strength for Hg on Pdn decorated PNG. Moreover, the charge transfer between Pdn and arsenic may constitute arsenic adsorption on Pdn decorated PNG. Further design of highly efficient carbon based sorbents for heavy metals removal should be focused on tailoring εd of adsorbed metals.

Remediation of arsenic-contaminated groundwater using media-injected permeable reactive barriers with a modified montmorillonite: sand tank studies.

PubMed

Luo, Ximing; Liu, Haifei; Huang, Guoxin; Li, Ye; Zhao, Yan; Li, Xu

2016-01-01

A modified montmorillonite (MMT) was prepared using an acid activation-sodium activation-iron oxide coating method to improve the adsorption capacities of natural MMTs. For MMT, its interlamellar distance increased from 12.29 to 13.36 Å, and goethite (α-FeOOH) was intercalated into its clay layers. Two novel media-injected permeable reactive barrier (MI-PRB) configurations were proposed for removing arsenic from groundwater. Sand tank experiments were conducted to investigate the performance of the two MI-PRBs: Tank A was filled with quartz sand. Tank B was packed with quartz sand and zero-valent iron (ZVI) in series, and the MMT slurry was respectively injected into them to form reactive zones. The results showed that for tank A, total arsenic (TA) removal of 98.57% was attained within the first 60 mm and subsequently descended slowly to 88.84% at the outlet. For tank B, a similar spatial variation trend was observed in the quartz sand layer, and subsequently, TA removal increased to ≥99.80% in the ZVI layer. TA removal by MMT mainly depended on both surface adsorption and electrostatic adhesion. TA removal by ZVI mainly relied on coagulation/precipitation and adsorption during the iron corrosion. The two MI-PRBs are feasible alternatives for in situ remediation of groundwater with elevated As levels.

Reactive polymer coatings: A robust platform towards sophisticated surface engineering for biotechnology

NASA Astrophysics Data System (ADS)

Chen, Hsien-Yeh

Functionalized poly(p-xylylenes) or so-called reactive polymers can be synthesized via chemical vapor deposition (CVD) polymerization. The resulting ultra-thin coatings are pinhole-free and can be conformally deposited to a wide range of substrates and materials. More importantly, the equipped functional groups can served as anchoring sites for tailoring the surface properties, making these reactive coatings a robust platform that can deal with sophisticated challenges faced in biointerfaces. In this work presented herein, surface coatings presenting various functional groups were prepared by CVD process. Such surfaces include aldehyde-functionalized coating to precisely immobilize saccharide molecules onto well-defined areas and alkyne-functionalized coating to click azide-modified molecules via Huisgen 1,3-dipolar cycloaddition reaction. Moreover, CVD copolymerization has been conducted to prepare multifunctional coatings and their specific functions were demonstrated by the immobilization of biotin and NHS-ester molecules. By using a photodefinable coating, polyethylene oxides were immobilized onto a wide range of substrates through photo-immobilization. Spatially controlled protein resistant properties were characterized by selective adsorption of fibrinogen and bovine serum albumin as model systems. Alternatively, surface initiator coatings were used for polymer graftings of polyethylene glycol) methyl ether methacrylate, and the resultant protein- and cell- resistant properties were characterized by adsorption of kinesin motor proteins, fibrinogen, and murine fibroblasts (NIH3T3). Accessibility of reactive coatings within confined microgeometries was systematically studied, and the preparation of homogeneous polymer thin films within the inner surface of microchannels was demonstrated. Moreover, these advanced coatings were applied to develop a dry adhesion process for microfluidic devices. This process provides (i) excellent bonding strength, (ii) extended

Adsorption kinetics of surfactants on activated carbon

NASA Astrophysics Data System (ADS)

Arnelli; Aditama, WP; Fikriani, Z.; Astuti, Y.

2018-04-01

A study on the adsorption of both cationic and anionic surfactants using activated carbon as well as the investigation of the adsorption isotherms and adsorption kinetics has been conducted. The results showed that the adsorption of sodium lauryl sulfate (SLS) by activated carbon was Langmuir’s adsorption isotherm while its adsorption kinetics showed pseudo-second order with an adsorption rate constant of 2.23 x 103 g mg-1 hour-1. Meanwhile, the adsorption of HDTMA-Br by activated carbon showed that the isotherm adsorption tended to follow Freundlich’s isotherm and was pseudo-second order with an adsorption rate constant of 89.39 g mg-1 hour-1.

Comparison of randomly cloned and whole genomic DNA probes for the detection of Porphyromonas gingivalis and Bacteroides forsythus

PubMed Central

Wong, M.; DiRienzo, J.M.; Lai, C.-H.; Listgarten, M. A.

2012-01-01

Whole genomic and randomly-cloned DNA probes for two fastidious periodontal pathogens, Porphyromonas gingivalis and Bacteroides forsythus were labeled with digoxigenin and detected by a colorimetric method. The specificity and sensitivity of the whole genomic and cloned probes were compared. The cloned probes were highly specific compared to the whole genomic probes. A significant degree of cross-reactivity with Bacteroides species. Capnocytophaga sp. and Prevotella sp. was observed with the whole genomic probes. The cloned probes were less sensitive than the whole genomic probes and required at least 106 target cells or a minimum of 10 ng of target DNA to be detected during hybridization. Although a ten-fold increase in sensitivity was obtained with the whole genomic probes, cross-hybridization to closely related species limits their reliability in identifying target bacteria in subgingival plaque samples. PMID:8636873

Strong Selective Adsorption of Polymers.

PubMed

Ge, Ting; Rubinstein, Michael

2015-06-09

A scaling theory is developed for selective adsorption of polymers induced by the strong binding between specific monomers and complementary surface adsorption sites. By "selective" we mean specific attraction between a subset of all monomers, called "sticky", and a subset of surface sites, called "adsorption sites". We demonstrate that, in addition to the expected dependence on the polymer volume fraction ϕ bulk in the bulk solution, selective adsorption strongly depends on the ratio between two characteristic length scales, the root-mean-square distance l between neighboring sticky monomers along the polymer, and the average distance d between neighboring surface adsorption sites. The role of the ratio l / d arises from the fact that a polymer needs to deform to enable the spatial commensurability between its sticky monomers and the surface adsorption sites for selective adsorption. We study strong selective adsorption of both telechelic polymers with two end monomers being sticky and multisticker polymers with many sticky monomers between sticky ends. For telechelic polymers, we identify four adsorption regimes at l / d < 1 that are characterized by the fraction of occupied adsorption sites and whether the dominant conformation of adsorbed chains is a single-end-adsorbed "mushroom" or double-end-adsorbed loop. For l / d > 1, we expect that the adsorption layer at exponentially low ϕ bulk consists of separated unstretched loops, while as ϕ bulk increases the layer crosses over to a brush of extended loops with a second layer of weakly overlapping tails. For multisticker chains, in the limit of exponentially low ϕ bulk , adsorbed polymers are well separated from each other. As l / d increases, the conformation of an individual polymer changes from a single-end-adsorbed "mushroom" to a random walk of loops. For high ϕ bulk , adsorbed polymers at small l / d are mushrooms that cover all the adsorption sites. At sufficiently large l / d , adsorbed multisticker

Challenges and Opportunities for Small-Molecule Fluorescent Probes in Redox Biology Applications.

PubMed

Jiang, Xiqian; Wang, Lingfei; Carroll, Shaina L; Chen, Jianwei; Wang, Meng C; Wang, Jin

2018-02-16

The concentrations of reactive oxygen/nitrogen species (ROS/RNS) are critical to various biochemical processes. Small-molecule fluorescent probes have been widely used to detect and/or quantify ROS/RNS in many redox biology studies and serve as an important complementary to protein-based sensors with unique applications. Recent Advances: New sensing reactions have emerged in probe development, allowing more selective and quantitative detection of ROS/RNS, especially in live cells. Improvements have been made in sensing reactions, fluorophores, and bioavailability of probe molecules. In this review, we will not only summarize redox-related small-molecule fluorescent probes but also lay out the challenges of designing probes to help redox biologists independently evaluate the quality of reported small-molecule fluorescent probes, especially in the chemistry literature. We specifically highlight the advantages of reversibility in sensing reactions and its applications in ratiometric probe design for quantitative measurements in living cells. In addition, we compare the advantages and disadvantages of small-molecule probes and protein-based probes. The low physiological relevant concentrations of most ROS/RNS call for new sensing reactions with better selectivity, kinetics, and reversibility; fluorophores with high quantum yield, wide wavelength coverage, and Stokes shifts; and structural design with good aqueous solubility, membrane permeability, low protein interference, and organelle specificity. Antioxid. Redox Signal. 00, 000-000.

Adsorption of nucleotides onto Fe-Mg-Al rich swelling clays

NASA Astrophysics Data System (ADS)

Feuillie, Cécile; Daniel, Isabelle; Michot, Laurent J.; Pedreira-Segade, Ulysse

2013-11-01

Mineral surfaces may have played a role in the origin of the first biopolymers, by concentrating organic monomers from a dilute ocean. Swelling clays provide a high surface area for the concentration of prebiotic monomers, and have therefore been the subject of numerous investigations. In that context, montmorillonite, the most abundant swelling clay in modern environments, has been extensively studied with regard to adsorption and polymerization of nucleic acids. However, montmorillonite was probably rather marginal on the primitive ocean floor compared to iron-magnesium rich phyllosilicates such as nontronite that results from the hydrothermal alteration of a mafic or ultramafic oceanic crust. In the present paper, we study the adsorption of nucleotides on montmorillonite and nontronite, at various pH and ionic strength conditions plausible for Archean sea-water. A thorough characterization of the mineral surfaces shows that nucleotide adsorb mainly on the edge faces of the smectites by ligand exchange between the phosphate groups of the nucleotides and the -OH groups from the edge sites over a wide pH range (4-10). Nontronite is more reactive than montmorillonite. At low pH, additional ion exchange may play a role as the nucleotides become positively charged.

Role of adsorption in liquid lubrication

NASA Technical Reports Server (NTRS)

Groszek, A. J.

1973-01-01

Changes at solid-liquid interfaces caused by adsorption from solution are discussed paying attention to the following aspects: (1) stability of adsorbed films and the structure of metal-additive-film-liquid interface and effect of adsorbate orientation. (2) chemical versus physical adsorption, (3) heat of adsorption, (4) adsorption of additives, (5) activated adsorption, effect of activating adsorbates, (6) displacement phenomena at solid-liquid interfaces, (7) competition of antiwear additives, their solvents, and water, (8) effect of adsorption on the orientation of liquid in the interfacial region, and (9) relation between the chemical nature of solid surfaces and their interaction with liquid lubricants. The relevance of the above adsorption phenomena to lubrication is discussed, referring where possible to specific examples.

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

PubMed

Pratt, C; Shilton, A

2009-01-01

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

ARSENIC TREATMENT BY ADSORPTIVE TECHNOLOGY

EPA Science Inventory

Presentation will discuss the removal of arsenic from drinking water using the adsorptive media treatment process. Fundamental information is provided on the design and operation of adsorptive media technology including the selection of the adsorptive media. The information cites...

An Isolable Phosphaethynolatoborane and Its Reactivity.

PubMed

Wilson, Daniel W N; Hinz, Alexander; Goicoechea, Jose M

2018-02-19

The synthesis and characterization of a stable phosphaethynolatoborane, [B]OCP (1, [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), is described. The increased triple bond character of the P-C bond in 1 relative to the free ion (PCO - ) is probed in a series of reactivity studies. Compound 1 readily dimerises in donor solvents to afford a cyclic five-membered 6π-aromatic compound, cyclo-P 2 {C[B]}O{CO[B]} (2), which decarbonylates on UV irradiation. By contrast the nickel-mediated dimerisation of 1 affords the isomeric diphosphacyclobutene [P(CO[B])] 2 . When 1 is reacted with organolithium reagents such as MesLi (Mes=2,4,6-trimethylphenyl), the boryl moiety shifts and the formation of the lithoxy-boryl-phosphaalkene [LiOC[B]P(Mes)] 2 was observed. The reactivity of this species towards electrophiles is also described. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Adsorption of aliphatic polyhydroxy carboxylic acids on gibbsite: pH dependency and importance of adsorbate structure.

PubMed

Schneckenburger, Tatjana; Riefstahl, Jens; Fischer, Klaus

2018-01-01

Aliphatic (poly)hydroxy carboxylic acids [(P)HCA] occur in natural, e.g. soils, and in technical (waste disposal sites, nuclear waste repositories) compartments . Their distribution, mobility and chemical reactivity, e.g. complex formation with metal ions and radionuclides, depend, among others, on their adsorption onto mineral surfaces. Aluminium hydroxides, e.g. gibbsite [α-Al(OH) 3 ], are common constituents of related solid materials and mimic the molecular surface properties of clay minerals. Thus, the study was pursued to characterize the adsorption of glycolic, threonic, tartaric, gluconic, and glucaric acids onto gibbsite over a wide pH and (P)HCA concentration range. To consider specific conditions occurring in radioactive wastes, adsorption applying an artificial cement pore water (pH 13.3) as solution phase was investigated additionally. The sorption of gluconic acid at pH 4, 7, 9, and 12 was best described by the "two-site" Langmuir isotherm, combining "high affinity" sorption sites (adsorption affinity constants [Formula: see text] > 1 L mmol -1 , adsorption capacities < 6.5 mmol kg -1 ) with "low affinity" sites ([Formula: see text] < 0.1 L mmol -1 , adsorption capacities ≥ 19 mmol kg -1 ). The total adsorption capacities at pH 9 and 12 were roughly tenfold of that at pH 4 and 7. The S-shaped pH sorption edge of gluconic acid was modelled applying a constant capacitance model, considering electrostatic interactions, hydrogen bonding, surface complex formation, and formation of solved polynuclear complexes between Al 3+ ions and gluconic acid. A Pearson and Spearman rank correlation between (P)HCA molecular properties and adsorption parameters revealed the high importance of the size and the charge of the adsorbates. The adsorption behaviour of (P)HCAs is best described by a combination of adsorption properties of carboxylic acids at acidic pH and of polyols at alkaline pH. Depending on the molecular properties of the adsorbates and

Molecular dynamics simulations of uranyl adsorption and structure on the basal surface of muscovite

DOE PAGES

Teich-McGoldrick, Stephanie L.; Greathouse, Jeffery A.; Cygan, Randall T.

2014-02-05

Anthropogenic activities have led to an increased concentration of uranium on the Earth’s surface and potentially in the subsurface with the development of nuclear waste repositories. Uranium is soluble in groundwater, and its mobility is strongly affected by the presence of clay minerals in soils and in subsurface sediments. We use molecular dynamics simulations to probe the adsorption of aqueous uranyl (UO 2 2+) ions onto the basal surface of muscovite, a suitable proxy for typically ultrafine-grained clay phases. Model systems include the competitive adsorption between potassium counterions and aqueous ions (0.1 M and 1.0 M UO 2Cl 2 ,more » 0.1 M NaCl). We find that for systems with potassium and uranyl ions present, potassium ions dominate the adsorption phenomenon. Potassium ions adsorb entirely as inner-sphere complexes associated with the ditrigonal cavity of the basal surface. Uranyl ions adsorb in two configurations when it is the only ion species present, and in a single configuration in the presence of potassium. Finally, the majority of adsorbed uranyl ions are tilted less than 45° relative to the muscovite surface, and are associated with the Si 4Al 2 rings near aluminum substitution sites.« less

Deficient crisis-probing practices and taken-for-granted assumptions in health organisations.

PubMed

Canyon, Deon V; Adhikari, Ashmita; Cordery, Thomas; Giguère-Simmonds, Philippe; Huang, Jessica; Nguyen, Helen; Watson, Michael; Yang, Daniel

2011-04-18

The practice of crisis-probing in proactive organisations involves meticulous and sustained investigation into operational processes and management structures for potential weaknesses and flaws before they become difficult to resolve. In health organisations, crisis probing is a necessary part of preparing to manage emerging health threats. This study examined the degree of pre-emptive probing in health organisations and the type of crisis training provided to determine whether or not they are prepared in this area. This evidence-based study draws on cross-sectional responses provided by executives from chiropractic, physiotherapy, and podiatry practices; dental and medical clinics; pharmacies; aged care facilities; and hospitals. The data show a marked lack of mandatory probing and a generalised failure to reward crisis reporting. Crisis prevention training is poor in all organisations except hospitals and aged care facilities where it occurs at an adequate frequency. However this training focuses primarily on natural disasters, fails to address most other crisis types, is mostly reactive and not designed to probe for and uncover key taken-for-granted assumptions. Crisis-probing in health organisations is inadequate, and improvements in this area may well translate into measurable improvements in preparedness and response outcomes.

Deficient crisis-probing practices and taken-for-granted assumptions in health organisations

PubMed Central

Canyon, Deon V.; Adhikari, Ashmita; Cordery, Thomas; Giguère-Simmonds, Philippe; Huang, Jessica; Nguyen, Helen; Watson, Michael; Yang, Daniel

2011-01-01

The practice of crisis-probing in proactive organisations involves meticulous and sustained investigation into operational processes and management structures for potential weaknesses and flaws before they become difficult to resolve. In health organisations, crisis probing is a necessary part of preparing to manage emerging health threats. This study examined the degree of pre-emptive probing in health organisations and the type of crisis training provided to determine whether or not they are prepared in this area. This evidence-based study draws on cross-sectional responses provided by executives from chiropractic, physiotherapy, and podiatry practices; dental and medical clinics; pharmacies; aged care facilities; and hospitals. The data show a marked lack of mandatory probing and a generalised failure to reward crisis reporting. Crisis prevention training is poor in all organisations except hospitals and aged care facilities where it occurs at an adequate frequency. However this training focuses primarily on natural disasters, fails to address most other crisis types, is mostly reactive and not designed to probe for and uncover key taken-for-granted assumptions. Crisis-probing in health organisations is inadequate, and improvements in this area may well translate into measurable improvements in preparedness and response outcomes. PMID:24149030

Method and apparatus for thermal swing adsorption and thermally-enhanced pressure swing adsorption

DOEpatents

Wegeng, Robert S.; Rassat, Scot D.; TeGrotenhuis, Ward E.; Drost, Kevin; Vishwanathan, Vilayanur V.

2004-06-08

The present invention provides compact adsorption systems that are capable of rapid temperature swings and rapid cycling. Novel methods of thermal swing adsorption and thermally-enhanced pressure swing adsorption are also described. In some aspects of the invention, a gas is passed through the adsorbent thus allowing heat exchangers to be very close to all portions of the adsorbent and utilize less space. In another aspect, the adsorption media is selectively heated, thus reducing energy costs. Methods and systems for gas adsorption/desorption having improved energy efficiency with capability of short cycle times are also described. In another aspect, the apparatus or methods utilize heat exchange channels of varying lengths that have volumes controlled to provide equal heat fluxes. Methods of fuel cell startup are also described. Advantages of the invention include the ability to use (typically) 30-100 times less adsorbent compared to conventional systems.

Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface

USGS Publications Warehouse

Power, L.E.; Arai, Y.; Sparks, D.L.

2005-01-01

Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

Influence of preozonation on the adsorptivity of humic substances onto activated carbon.

PubMed

Rodríguez, Francisco J; García-Valverde, María

2016-11-01

This research aims to study the influence of preozonation on the adsorptivity of humic substances onto activated carbon, which are usual stages in drinking water treatment. Three different types of humic substances were used in this study: natural fulvic and humic acids extracted from the Úzquiza Reservoir (Burgos, Spain) and a commercially supplied humic acid. The fractionation of the humic substances by ultrafiltration showed a very different molecular weight (MW) distribution for them: the lowest fraction of <1 kDa comprises the vast majority of the fulvic acids (around 86 %), whereas the main fraction for the commercial humic acids was the highest one of >30 kDa (around 40 %). The natural humic acids show an intermediate distribution between the two aforementioned humic substances. The 1-5-kDa fraction turned out to be the most reactive toward trihalomethane formation for the commercial humic acids. The adsorptive capacity of activated carbon for the humic substances was in the following order: natural fulvic acids > natural humic acids > commercial humic acids. The most adsorbable fraction was that of <1 kDa for the fulvic acids, whereas the 5-10-kDa fraction was the most adsorbable for both humic acids. Preozonation changes the MW distribution of the humic substances, decreasing the abundance of the high MW fractions and generating smaller molecules within the low to medium MW range. Adsorption isotherms show that preozonation has a beneficial effect on the adsorptivity of the commercial humic acids onto activated carbon, whereas no appreciable effect was observed for the case of the fulvic acids.

Synthesis of low-cost adsorbent from rice bran for the removal of reactive dye based on the response surface methodology

NASA Astrophysics Data System (ADS)

Hong, Gui-Bing; Wang, Yi-Kai

2017-11-01

Rice bran is a major by-product of the rice milling industry and is abundant in Taiwan. This study proposed a simple method for modifying rice bran to make it a low-cost adsorbent to remove reactive blue 4 (RB4) from aqueous solutions. The effects of independent variables such as dye concentration (100-500 ppm), adsorbent dosage (20-120 mg) and temperature (30-60 °C) on the dye adsorption capacity of the modified rice bran adsorbent were investigated by using the response surface methodology (RSM). The results showed that the dye maximum adsorption capacity of the modified rice bran adsorbent was 151.3 mg g-1 with respect to a dye concentration of 500 ppm, adsorbent dosage of 65.36 mg, and temperature of 60 °C. The adsorption kinetics data followed the pseudo-second-order kinetic model, and the isotherm data fit the Langmuir isotherm model well. The maximum monolayer adsorption capacity was 178.57-185.19 mg g-1, which was comparable to that of other agricultural waste adsorbents used to remove RB4 from aqueous solutions in the literature. The thermodynamics analysis results indicated that the adsorption of RB4 onto the modified rice bran adsorbent is an endothermic, spontaneous monolayer adsorption that occurs through a physical process.

Adsorption of organic chemicals in soils.

PubMed Central

Calvet, R

1989-01-01

This paper presents a review on adsorption of organic chemicals on soils sediments and their constituents. The first part of this review deals with adsorption from gas and liquid phases and gives a discussion on the physical meaning of the shape of adsorption isotherms. Results show that no general rules can be proposed to describe univocally the relation between the shape of isotherms and the nature of adsorbate-adsorbent system. Kinetics of adsorption is discussed through the description of various models. Theoretical developments exist both for the thermodynamics and the kinetics of adsorption, but there is a strong need for experimental results. Possible adsorption mechanisms are ion exchange, interaction with metallic cations, hydrogen bonds, charge transfers, and London-van der Waals dispersion forces/hydrophobic effect. However, direct proofs of a given mechanism are rare. Several factors influence adsorption behavior. Electronic structure of adsorbed molecules, properties of adsorbents, and characteristics of the liquid phase are discussed in relation to adsorption. Such properties as water solubility, organic carbon content of adsorbing materials, and the composition of the liquid phase are particularly important. Evaluation of adsorption can be obtained through either laboratory measurements or use of several correlations. Adsorption measurements must be interpreted, taking into account treatment of adsorbent materials, experimental conditions, and secondary phenomena such as degradations. Correlations between adsorption coefficients and water-octanol partition coefficient or water solubility are numerous. They may be useful tools for prediction purposes. Relations with transport, bioavailability, and degradation are described. PMID:2695323

Structure reactivity relationships during N2O hydrogenation over Au-Ag alloys: A study by field emission techniques

NASA Astrophysics Data System (ADS)

Jacobs, Luc; Barroo, Cédric; Gilis, Natalia; Lambeets, Sten V.; Genty, Eric; Visart de Bocarmé, Thierry

2018-03-01

To make available atomic oxygen at the surface of a catalyst is the key step for oxidation reactions on Au-based catalysts. In this context, Au-Ag alloys catalysts exhibit promising properties for selective oxidation reactions of alcohols: low temperature activity and high selectivity. The presence of O(ads) and its effects on the catalytic reactivity is studied via the N2O dissociative adsorption and subsequent hydrogenation. Field emission techniques are particularly suited to study this reaction: Field Ion Microscopy (FIM) and Field Emission Microscopy (FEM) enable to image the extremity of sharp metallic tips, the size and morphology of which are close to those of one single catalytic particle. The reaction dynamics is studied in the 300-320 K temperature range and at a pressure of 3.5 × 10-3 Pa. The main results are a strong structure/reactivity relationship during N2O + H2 reaction over Au-8.8 at.%Ag model catalysts. Comparison of high-resolution FIM images of the clean sample and FEM images during reaction shows a sensitivity of the reaction to the local structure of the facets, independently of the used partial pressures of both N2O and H2. This suggests a localised dissociative adsorption step for N2O and H2 with the formation of a reactive interface around the {210} facets.

Method and apparatus for measuring reactivity of fissile material

DOEpatents

Lee, David M.; Lindquist, Lloyd O.

1985-01-01

Given are a method and apparatus for measuring nondestructively and non-invasively (i.e., using no internal probing) the burnup, reactivity, or fissile content of any material which emits neutrons and which has fissionable components. No external neutron-emitting interrogation source or fissile material is used and no scanning is required, although if a profile is desired scanning can be used. As in active assays, here both reactivity and content of fissionable material can be measured. The assay is accomplished by altering the return flux of neutrons into the fuel assembly. The return flux is altered by changing the reflecting material. The existing passive neutron emissions in the material being assayed are used as the source of interrogating neutrons. Two measurements of either emitted neutron or emitted gamma-ray count rates are made and are then correlated to either reactivity, burnup, or fissionable content of the material being assayed, thus providing a measurement of either reactivity, burnup, or fissionable content of the material being assayed. Spent fuel which has been freshly discharged from a reactor can be assayed using this method and apparatus. Precisions of 1000 MWd/tU appear to be feasible.

Reactive transport of metal contaminants in alluvium - Model comparison and column simulation

USGS Publications Warehouse

Brown, J.G.; Bassett, R.L.; Glynn, P.D.

2000-01-01

A comparative assessment of two reactive-transport models, PHREEQC and HYDROGEOCHEM (HGC), was done to determine the suitability of each for simulating the movement of acidic contamination in alluvium. For simulations that accounted for aqueous complexation, precipitation and dissolution, the breakthrough and rinseout curves generated by each model were similar. The differences in simulated equilibrium concentrations between models were minor and were related to (1) different units in model output, (2) different activity coefficients, and (3) ionic-strength calculations. When adsorption processes were added to the models, the rinseout pH simulated by PHREEQC using the diffuse double-layer adsorption model rose to a pH of 6 after pore volume 15, about 1 pore volume later than the pH simulated by HGC using the constant-capacitance model. In PHREEQC simulation of a laboratory column experiment, the inability of the model to match measured outflow concentrations of selected constituents was related to the evident lack of local geochemical equilibrium in the column. The difference in timing and size of measured and simulated breakthrough of selected constituents indicated that the redox and adsorption reactions in the column occurred slowly when compared with the modeled reactions. MINTEQA2 and PHREEQC simulations of the column experiment indicated that the number of surface sites that took part in adsorption reactions was less than that estimated from the measured concentration of Fe hydroxide in the alluvium.

Elimination of reactive blue 4 from aqueous solutions using 3-aminopropyl triethoxysilane modified chitosan beads.

PubMed

Vakili, Mohammadtaghi; Rafatullah, Mohd; Salamatinia, Babak; Ibrahim, Mahamad Hakimi; Abdullah, Ahmad Zuhairi

2015-11-05

The adsorption behavior of chitosan (CS) beads modified with 3-aminopropyl triethoxysilane (APTES) for the removal of reactive blue 4 (RB4) in batch studies has been investigated. The effects of modification conditions, such as the APTES concentration, temperature and reaction time on RB4 removal, were studied. The adsorbent prepared at a concentration of 2 wt% APTES for 8h at 50 °C was the most effective one for RB4 adsorption. The adsorption capacity of modified CS beads (433.77 mg/g) was 1.37 times higher than that of unmodified CS beads (317.23 mg/g). The isotherm data are adequately described by a Freundlich model, and the kinetic study revealed that the pseudo-second-order rate model was in better agreement with the experimental data. The negative values of the thermodynamic parameters, including ΔG° (-2.28 and -4.70 kJ/mol at 30 ± 2 °C), ΔH° (-172.18 and -43.82 kJ/mol) and ΔS° (-560.71 and -129.08 J/mol K) for CS beads and APTES modified beads, respectively, suggest that RB4 adsorption is a spontaneous and exothermic process. Copyright © 2015 Elsevier Ltd. All rights reserved.

Axial vs. Equatorial Ligand Rivalry in Controlling the Reactivity of Iron(IV)-Oxo Species: Single-State vs. Two-State Reactivity.

PubMed

Kumar, Ravi; Ansari, Azaj; Rajaraman, Gopalan

2018-05-07

High-valent iron-oxo species are known for their very high reactivity, and this aspect has been studied in detail over the years. The role of axial ligands in fine-tuning the reactivity of the iron(IV)-oxo species has been particularly well studied. The corresponding role of equatorial ligands, however, has rarely been explored, and is of prime importance in the development of non-heme chemistry. Here, we have undertaken detailed DFT calculations on [(L NHC )Fe IV (O)(CH 3 CN)] 2+ (1; L NHC =3,9,14,20-tetraaza1,6,12,17-tetraazoniapenta-cyclohexacosane-1(23),4,6(26),10,12(25),15,17(24),21-octaene) in comparison to compound II of cytochrome P450 [(porphyrin)Fe IV (O)(SH)] - (2) to probe this aspect. The electronic structures of 1 and 2 are found to vary significantly, implying a large variation in their reactivities. In particular, the strong equatorial ligand present in 1 significantly destabilizes the quintet states as compared to species 2. To fully understand the reactivity pattern of these species, we have modelled the hydroxylation of methane by both 1 and 2. Our calculations reveal that 1 reacts via a low-lying S=1 π pathway, and that the generally available S=2 σ pathway is not energetically accessible. In addition to having a significant barrier for C-H bond activation, the -OH rebound step is also computed to have a large barrier height, leading to a marked difference in reactivity between these two species. Of particular relevance here is the observation of pure triplet-state reactivity for 1. We have also attempted to test the role of axial ligands in fine-tuning the reactivity of 1, and our results demonstrate that, in contrast to heme systems, the axial ligands in 1 do not significantly influence the reactivity. This highlights the importance of designing equatorial ligands to fine-tune reactivity of high-valent iron(IV)-oxo species. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Methane and CO2 Adsorption Capacities of Kerogen in the Eagle Ford Shale from Molecular Simulation.

PubMed

Psarras, Peter; Holmes, Randall; Vishal, Vikram; Wilcox, Jennifer

2017-08-15

Over the past decade, the United States has become a world leader in natural gas production, thanks in part to a large-fold increase in recovery from unconventional resources, i.e., shale rock and tight oil reservoirs. In an attempt to help mitigate climate change, these depleted formations are being considered for their long-term CO 2 storage potential. Because of the variability in mineral and structural composition from one formation to the next (even within the same region), it is imperative to understand the adsorption behavior of CH 4 and CO 2 in the context of specific conditions and pore surface chemistry, i.e., relative total organic content (TOC), clay, and surface functionality. This study examines two Eagle Ford shale samples, both recovered from shale that was extracted at depths of approximately 3800 m and having low clay content (i.e., less than 5%) and similar mineral compositions but distinct TOCs (i.e., 2% and 5%, respectively). Experimentally validated models of kerogen were used to the estimate CH 4 and CO 2 adsorption capacities. The pore size distributions modeled were derived from low-pressure adsorption isotherm data using CO 2 and N 2 as probe gases for micropores and mesopores, respectively. Given the presence of water in these natural systems, the role of surface chemistry on modeled kerogen pore surfaces was investigated. Several functional groups associated with surface-dissociated water were considered. Pressure conditions from 10 to 50 bar were investigated using grand canonical Monte Carlo simulations along with typical outgassing temperatures used in many shale characterization and adsorption studies (i.e., 60 and 250 °C). Both CO 2 and N 2 were used as probe gases to determine the total pore volume available for gas adsorption spanning pore diameters ranging from 0.3 to 30 nm. The impacts of surface chemistry, outgassing temperature, and the inclusion of nanopores with diameters of less than 1.5 nm were determined for applications

Adsorption of multi-heavy metals Zn and Cu onto surficial sediments: modeling and adsorption capacity analysis.

PubMed

Li, Shanshan; Zhang, Chen; Wang, Meng; Li, Yu

2014-01-01

Improved multiple regression adsorption models (IMRAMs) was developed to estimate the adsorption capacity of the components [Fe oxides (Fe), Mn oxides (Mn), organic materials (OMs), residuals] in surficial sediments for multi-heavy metal Zn and Cu. IMRAM is an improved version over MRAM, which introduces a computer program in the model developing process. As MRAM, Zn(Cu) IMRAM, and Cu(Zn) IMRAM again confirmed that there is significant interaction effects that control the adsorption of compounded Zn and Cu, which was neglected by additional adsorption model. The verification experiment shows that the relative deviation of the IMRAMs is less than 13%. It is revealed by the IMRAMs that Mn, which has the greatest adsorption capability for compounded Zn and Cu (54.889 and 161.180 mg/l, respectively), follows by interference adsorption capacity of Fe/Mn (-1.072 and -24.591 mg/l respectively). Zn and Cu influence each other through different mechanisms. When Zn is the adsorbate, compounded Cu mainly affects the adsorption capacities of Fe/Mn and Fe/Mn/OMs; while when Cu is the adsorbate, compounded Zn mainly exerts its effect on Mn, Fe/Mn, and Mn/OMs. It also shows that the compounded Zn or Cu weakened the interference adsorption of Fe/Mn, and meanwhile, strengthened the interference adsorption of Mn/OMs.

Probing thyroglobulin in undiluted human serum based on pattern recognition and competitive adsorption of proteins

NASA Astrophysics Data System (ADS)

Wang, Ran; Huang, Shuai; Li, Jing; Chae, Junseok

2014-10-01

Thyroglobulin (Tg) is a sensitive indicator of persistent or recurrent differentiated thyroid cancer of follicular cell origin. Detection of Tg in human serum is challenging as bio-receptors, such as anti-Tg, used in immunoassay have relatively weak binding affinity. We engineer sensing surfaces using the competitive adsorption of proteins, termed the Vroman Effect. Coupled with Surface Plasmon Resonance, the "cross-responsive" interactions of Tg on the engineered surfaces produce uniquely distinguishable multiple signature patterns, which are discriminated using Linear Discriminant Analysis. Tg-spiked samples, down to 2 ng/ml Tg in undiluted human serum, are sensitively and selectively discriminated from the control (undiluted human serum).

Surface Complexation Modeling of Fluoride Adsorption by Soil and the Role of Dissolved Aluminum on Adsorption

NASA Astrophysics Data System (ADS)

Padhi, S.; Tokunaga, T.

2017-12-01

Adsorption of fluoride (F) on soil can control the mobility of F and subsequent contamination of groundwater. Hence, accurate evaluation of adsorption equilibrium is a prerequisite for understanding transport and fate of F in the subsurface. While there have been studies for the adsorption behavior of F with respect to single mineral constituents based on surface complexation models (SCM), F adsorption to natural soil in the presence of complexing agents needs much investigation. We evaluated the adsorption processes of F on a natural granitic soil from Tsukuba, Japan, as a function of initial F concentration, ionic strength, and initial pH. A SCM was developed to model F adsorption behavior. Four possible surface complexation reactions were postulated with and without including dissolved aluminum (Al) and Al-F complex sorption. Decrease in F adsorption with the increase in initial pH was observed in between the initial pH range of 4 to 9, and a decrease in the rate of the reduction of adsorbed F with respect to the increase in the initial pH was observed in the initial pH range of 5 to 7. Ionic strength variation in the range of 0 to 100mM had insignificant effect on F removal. Changes in solution pH were observed by comparing the solution before and after F adsorption experiments. At acidic pH, the solution pH increased, whereas at alkaline pH, the solution pH decreased after equilibrium. The SCM including dissolved Al and the adsorption of Al-F complex can simulate the experimental results quite successfully. Also, including dissolved Al and the adsorption of Al-F complex to the model explained the change in solution pH after F adsorption.

Adsorption of nucleotides on biomimetic apatite: The case of adenosine 5⿲ triphosphate (ATP)

NASA Astrophysics Data System (ADS)

Hammami, Khaled; El-Feki, Hafed; Marsan, Olivier; Drouet, Christophe

2016-01-01

ATP is a well-known energy supplier in cells. The idea to associate ATP to pharmaceutical formulations/biotechnological devices to promote cells activity by potentially modulating their microenvironment thus appears as an appealing novel approach. Since biomimetic nanocrystalline apatites have shown great promise for biomedical applications (bone regeneration, cells diagnostics/therapeutics, ⿦), thanks to a high surface reactivity and an intrinsically high biocompatibility, the present contribution was aimed at exploring ATP/apatite interactions. ATP adsorption on a synthetic carbonated nanocrystalline apatite preliminarily characterized (by XRD, FTIR, Raman, TG-DTA and SEM-EDX) was investigated in detail, pointing out a good agreement with Sips isothermal features. Adsorption characteristics were compared to those previously obtained on monophosphate nucleotides (AMP, CMP), unveiling some specificities. ATP was found to adsorb effectively onto biomimetic apatite: despite smaller values of the affinity constant KS and the exponential factor m, larger adsorbed amounts were reached for ATP as compared to AMP for any given concentration in solution. m < 1 suggests that the ATP/apatite adsorption process is mostly guided by direct surface bonding rather than through stabilizing intermolecular interactions. Although standard οGads ° was estimated to only ⿿4 kJ/mol, the large value of Nmax led to significantly negative effective οGads values down to ⿿33 kJ/mol, reflecting the spontaneous character of adsorption process. Vibrational spectroscopy data (FTIR and Raman) pointed out spectral modifications upon adsorption, confirming chemical-like interactions where both the triphosphate group of ATP and its nucleic base were involved. The present study is intended to serve as a basis for future research works involving ATP and apatite nanocrystals/nanoparticles in view of biomedical applications (e.g. bone tissue engineering, intracellular drug delivery, ⿦).

The Development of Fluorescent Probes for Visualizing Intracellular Hydrogen Polysulfides.

PubMed

Chen, Wei; Rosser, Ethan W; Matsunaga, Tetsuro; Pacheco, Armando; Akaike, Takaaki; Xian, Ming

2015-11-16

Endogenous hydrogen polysulfides (H2Sn; n>1) have been recognized as important regulators in sulfur-related redox biology. H2Sn can activate tumor suppressors, ion channels, and transcription factors with higher potency than H2S. Although H2Sn are drawing increasing attention, their exact mechanisms of action are still poorly understood. A major hurdle in this field is the lack of reliable and convenient methods for H2Sn detection. Herein we report a H2Sn-mediated benzodithiolone formation under mild conditions. This method takes advantage of the unique dual reactivity of H2Sn as both a nucleophile and an electrophile. Based on this reaction, three fluorescent probes (PSP-1, PSP-2, and PSP-3) were synthesized and evaluated. Among the probes prepared, PSP-3 showed a desirable off/on fluorescence response to H2Sn and high specificity. The probe was successfully applied in visualizing intracellular H2Sn. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A revised design for microarray experiments to account for experimental noise and uncertainty of probe response.

PubMed

Pozhitkov, Alex E; Noble, Peter A; Bryk, Jarosław; Tautz, Diethard

2014-01-01

Although microarrays are analysis tools in biomedical research, they are known to yield noisy output that usually requires experimental confirmation. To tackle this problem, many studies have developed rules for optimizing probe design and devised complex statistical tools to analyze the output. However, less emphasis has been placed on systematically identifying the noise component as part of the experimental procedure. One source of noise is the variance in probe binding, which can be assessed by replicating array probes. The second source is poor probe performance, which can be assessed by calibrating the array based on a dilution series of target molecules. Using model experiments for copy number variation and gene expression measurements, we investigate here a revised design for microarray experiments that addresses both of these sources of variance. Two custom arrays were used to evaluate the revised design: one based on 25 mer probes from an Affymetrix design and the other based on 60 mer probes from an Agilent design. To assess experimental variance in probe binding, all probes were replicated ten times. To assess probe performance, the probes were calibrated using a dilution series of target molecules and the signal response was fitted to an adsorption model. We found that significant variance of the signal could be controlled by averaging across probes and removing probes that are nonresponsive or poorly responsive in the calibration experiment. Taking this into account, one can obtain a more reliable signal with the added option of obtaining absolute rather than relative measurements. The assessment of technical variance within the experiments, combined with the calibration of probes allows to remove poorly responding probes and yields more reliable signals for the remaining ones. Once an array is properly calibrated, absolute quantification of signals becomes straight forward, alleviating the need for normalization and reference hybridizations.

Probing the Adsorption of Carbon Monoxide on Transition Metal Clusters Using IR Action Spectroscopy

NASA Astrophysics Data System (ADS)

Lapoutre, Vivike J. F.; Oomens, Jos; Bakker, Joost M.

2012-06-01

The discovery of enhanced catalytic activity of small gold clusters has led to a great interest in size-dependent catalytic properties of metal clusters. To obtain a better understanding of the catalytic mechanisms it is essential to know the structures of these clusters and the nature of their interaction with reactant molecules. We have studied the structure of gas-phase niobium clusters with a carbon monoxide adsorbed using IR action spectroscopy. We present size-selective IR spectra obtained via IR multiple photon spectroscopy monitoring either photodetachment or photodissociation depending on the charge state. The combination of these spectra with DFT calculations allows for the structural determination of the adsorption product. M. Haruta et al., Journal of Catalysis 115 301-309 (1989). M. Haertelt et al., The Journal of Physical Chemistry Letters 2 1720-1724 (2011)

Adsorption and Exchange Dynamics in Aging Hydroxyethylcellulose Layers on Silica.

PubMed

Mubarekyan; Santore

2000-07-15

The adsorption kinetics of hydroxyethylcellulose (HEC) on silica and relaxations in adsorbed HEC layers were probed using total internal reflectance fluorescence and near-Brewster reflectivity. Like many random-coil polymers, HEC was found to adsorb at the transport-limited rate. Relaxations occurred at nearly constant interfacial mass when HEC layers were exposed to aqueous solvent, causing the subsequent exchange of chains between the layer and the free solution to become increasingly hindered. Eventually, on the time scale of a day, layers became immobilized and unable to accommodate chains from free solution. A continued fluorescence decay, beyond time scales that could be probed with self exchange, suggested further relaxations of the adsorbed HEC. The polydisperse HEC system (with an average molecular weight near 450,000) behaved qualitatively similar to molecular weight standard polyethylene oxide (PEO) layers on silica. For instance, relaxations in PEO layers occurred on a time scale of 10-20 h, like the HEC layers. Young layers of the latter, however, exhibited self-exchange kinetics that were an order of magnitude slower than PEO layers of similar age. This difference in adsorbed layer dynamics was attributed to HEC's stiffer backbone, compared with flexible PEO. Copyright 2000 Academic Press.

Biased-probe-induced water ion injection into amorphous polymers investigated by electric force microscopy

NASA Astrophysics Data System (ADS)

Knorr, Nikolaus; Rosselli, Silvia; Miteva, Tzenka; Nelles, Gabriele

2009-06-01

Although charging of insulators by atomic force microscopy (AFM) has found widespread interest, often with data storage or nanoxerography in mind, less attention has been paid to the charging mechanism and the nature of the charge. Here we present a systematic study on charging of amorphous polymer films by voltage pulses applied to conducting AFM probes. We find a quadratic space charge limited current law of Kelvin probe force microscopy and electrostatic force microscopy peak volumes in pulse height, offset by a threshold voltage, and a power law in pulse width of positive exponents smaller than one. We interpret the results by a charging mechanism of injection and surface near accumulation of aqueous ions stemming from field induced water adsorption, with threshold voltages linked to the water affinities of the polymers.

Grafting of aniline derivatives onto chitosan and their applications for removal of reactive dyes from industrial effluents.

PubMed

Abbasian, Mojtaba; Jaymand, Mehdi; Niroomand, Pouneh; Farnoudian-Habibi, Amir; Karaj-Abad, Saber Ghasemi

2017-02-01

A series of chitosan-grafted polyaniline derivatives {chitosan-g-polyaniline (CS-g-PANI), chitosan-g-poly(N-methylaniline) (CS-g-PNMANI), and chitosan-g-poly(N-ethylaniline) (CS-g-PNEANI)} were synthesized by in situ chemical oxidation polymerization method. The synthesized copolymers were analyzed by means of Fourier transform infrared (FTIR), and ultraviolet-visible (UV-vis) spectroscopies, thermogravimetric analysis (TGA), and field emission scanning electron microscopy (FE-SEM). These copolymers were applied as adsorbent for removal of acid red 4 (AR4) and direct red 23 (DR23) from aqueous solutions. The adsorption processes were optimized in terms of pH, adsorbent amount, and dyes concentrations. The maximum adsorption capacities (Q m ) for the synthesized copolymers were calculated, and among them the CS-g-PNEANI sample showed highest Q m for both AR4 (98mgg -1 ) and DR23 (112mgg -1 ) dyes. The adsorption kinetics of AR4 and DR23 dyes follow the pseudo-second order kinetic model. The regeneration and reusability tests revealed that the synthesized adsorbents had the relatively good reusability after five repetitions of the adsorption-desorption cycles. As the results, it is expected that the CS-g-PANIs find application for removal of reactive dyes (especially anionic dyes) from industrial effluents mainly due to their low production costs and high adsorption effectiveness. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Gas-phase formaldehyde adsorption isotherm studies on activated carbon: correlations of adsorption capacity to surface functional group density.

PubMed

Carter, Ellison M; Katz, Lynn E; Speitel, Gerald E; Ramirez, David

2011-08-01

Formaldehyde (HCHO) adsorption isotherms were developed for the first time on three activated carbons representing one activated carbon fiber (ACF) cloth, one all-purpose granular activated carbon (GAC), and one GAC commercially promoted for gas-phase HCHO removal. The three activated carbons were evaluated for HCHO removal in the low-ppm(v) range and for water vapor adsorption from relative pressures of 0.1-0.9 at 26 °C where, according to the IUPAC isotherm classification system, the adsorption isotherms observed exhibited Type V behavior. A Type V adsorption isotherm model recently proposed by Qi and LeVan (Q-L) was selected to model the observed adsorption behavior because it reduces to a finite, nonzero limit at low partial pressures and it describes the entire range of adsorption considered in this study. The Q-L model was applied to a polar organic adsorbate to fit HCHO adsorption isotherms for the three activated carbons. The physical and chemical characteristics of the activated carbon surfaces were characterized using nitrogen adsorption isotherms, X-ray photoelectron spectroscopy (XPS), and Boehm titrations. At low concentrations, HCHO adsorption capacity was most strongly related to the density of basic surface functional groups (SFGs), while water vapor adsorption was most strongly influenced by the density of acidic SFGs.

Adsorption of antibiotics on microplastics.

PubMed

Li, Jia; Zhang, Kaina; Zhang, Hua

2018-06-01

Microplastics and antibiotics are two classes of emerging contaminants with proposed negative impacts to aqueous ecosystems. Adsorption of antibiotics on microplastics may result in their long-range transport and may cause compound combination effects. In this study, we investigated the adsorption of 5 antibiotics [sulfadiazine (SDZ), amoxicillin (AMX), tetracycline (TC), ciprofloxacin (CIP), and trimethoprim (TMP)] on 5 types of microplastics [polyethylene (PE), polystyrene (PS), polypropylene (PP), polyamide (PA), and polyvinyl chloride (PVC)] in the freshwater and seawater systems. Scanning Electron Microscope (SEM) and X-ray diffractometer (XRD) analysis revealed that microplastics have different surface characterizes and various degrees of crystalline. Adsorption isotherms demonstrated that PA had the strongest adsorption capacity for antibiotics with distribution coefficient (K d ) values ranged from 7.36 ± 0.257 to 756 ± 48.0 L kg -1 in the freshwater system, which can be attributed to its porous structure and hydrogen bonding. Relatively low adsorption capacity was observed on other four microplastics. The adsorption amounts of 5 antibiotics on PS, PE, PP, and PVC decreased in the order of CIP > AMX > TMP > SDZ > TC with K f correlated positively with octanol-water partition coefficients (Log K ow ). Comparing to freshwater system, adsorption capacity in seawater decreased significantly and no adsorption was observed for CIP and AMX. Our results indicated that commonly observed polyamide particles can serve as a carrier of antibiotics in the aquatic environment. Copyright © 2018 Elsevier Ltd. All rights reserved.

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

Charge-controlled switchable CO adsorption on FeN4 cluster embedded in graphene

NASA Astrophysics Data System (ADS)

Omidvar, Akbar

2018-02-01

Electrical charging of an FeN4 cluster embedded in graphene (FeN4G) is proposed as an approach for electrocatalytically switchable carbon monoxide (CO) adsorption. Using density functional theory (DFT), we found that the CO molecule is strongly adsorbed on the uncharged FeN4G cluster. Our results show that the adsorption energy of a CO molecule on the FeN4G cluster is dramatically decreased by introducing extra electrons into the cluster. Once the charges are removed, the CO molecule is spontaneously adsorbed on the FeN4G absorbent. In the framework of frontier molecular orbital (FMO) analysis, the enhanced sensitivity and reactivity of the FeN4G cluster towards the CO molecule can be interpreted in terms of interaction between the HOMO of CO molecule and the LUMO of FeN4G cluster. Therefore, this approach promises both facile reversibility and tunable kinetics without the need of specific catalysts. Our study indicates that the FeN4G nanomaterial is an excellent absorbent for controllable and reversible capture and release of the CO.

Fluorescent Probes for Sensing and Imaging within Specific Cellular Organelles.

PubMed

Zhu, Hao; Fan, Jiangli; Du, Jianjun; Peng, Xiaojun

2016-10-18

Fluorescent probes have become powerful tools in biosensing and bioimaging because of their high sensitivity, specificity, fast response, and technical simplicity. In the last decades, researchers have made remarkable progress in developing fluorescent probes that respond to changes in microenvironments (e.g., pH, viscosity, and polarity) or quantities of biomolecules of interest (e.g., ions, reactive oxygen species, and enzymes). All of these analytes are specialized to carry out vital functions and are linked to serious disorders in distinct subcellular organelles. Each of these organelles plays a specific and indispensable role in cellular processes. For example, the nucleus regulates gene expression, mitochondria are responsible for aerobic metabolism, and lysosomes digest macromolecules for cell recycling. A certain organelle requires specific biological species and the appropriate microenvironment to perform its cellular functions, while breakdown of the homeostasis of biomolecules or microenvironmental mutations leads to organelle malfunctions, which further cause disorders or diseases. Fluorescent probes that can be targeted to both specific organelles and biochemicals/microenvironmental factors are capable of reporting localized bioinformation and are potentially useful for gaining insight into the contributions of analytes to both healthy and diseased states. In this Account, we review our recent work on the development of fluorescent probes for sensing and imaging within specific organelles. We present an overview of the design, photophysical properties, and biological applications of the probes, which can localize to mitochondria, lysosomes, the nucleus, the Golgi apparatus, and the endoplasmic reticulum. Although a diversity of organelle-specific fluorescent stains have been commercially available, our efforts place an emphasis on improvements in terms of low cytotoxicity, high photostability, near-infrared (NIR) emission, two-photon excitation, and

Automatic Processing of Reactive Polymers

NASA Technical Reports Server (NTRS)

Roylance, D.

1985-01-01

A series of process modeling computer codes were examined. The codes use finite element techniques to determine the time-dependent process parameters operative during nonisothermal reactive flows such as can occur in reaction injection molding or composites fabrication. The use of these analytical codes to perform experimental control functions is examined; since the models can determine the state of all variables everywhere in the system, they can be used in a manner similar to currently available experimental probes. A small but well instrumented reaction vessel in which fiber-reinforced plaques are cured using computer control and data acquisition was used. The finite element codes were also extended to treat this particular process.

Removal of lead(II) by adsorption using treated granular activated carbon: batch and column studies.

PubMed

Goel, Jyotsna; Kadirvelu, Krishna; Rajagopal, Chitra; Kumar Garg, Vinod

2005-10-17

In the present study, a deeper understanding of adsorption behavior of Pb(II) from aqueous systems onto activated carbon and treated activated carbon has been attempted via static and column mode studies under various conditions. It probes mainly two adsorbents that is, activated carbon (AC) and modified activated carbon (AC-S). Characterization of both the adsorbents was one of the key focal areas of the present study. This has shown a clear change or demarcation in the various physical and chemical properties of the modified adsorbent from its precursor activated carbon. Both the adsorbents are subjected to static mode adsorption studies and then after a comparison based on isotherm analysis; more efficient adsorbent is screened for column mode adsorption studies. The lead removal increased for sample of treated carbon. The extent of Pb(II) removal was found to be higher in the treated activated carbon. The aim of carrying out the continuous-flow studies was to assess the effect of various process variables, viz., of bed height, hydraulic loading rate and initial feed concentration on breakthrough time and adsorption capacity. This has helped in ascertaining the practical applicability of the adsorbent. Breakthrough curves were plotted for the adsorption of lead on the adsorbent using continuous-flow column operation by varying different operating parameters like hydraulic loading rate (3.0-10.5 m3/(hm2)), bed height (0.3-0.5 m) and feed concentrations (2.0-6.0 mg/l). At the end, an attempt has also been made to model the data generated from column studies using the empirical relationship based on Bohart-Adams model. This model has provided an objective framework to the subjective interpretation of the adsorption system and the model constant obtained here can be used to achieve the ultimate objective of our study that is, up scaling and designing of adsorption process at the pilot plant scale level. AC-S column regeneration using 0.5 and 1.0M concentration of

The formation of reactive species having hydroxyl radical-like reactivity from UV photolysis of N-nitrosodimethylamine (NDMA): kinetics and mechanism.

PubMed

Kwon, Bum Gun; Kim, Jong-Oh; Namkung, Kyu Cheol

2012-10-15

This study focuses on the detailed mechanism by which N-nitrosodimethylamine (NDMA) is photolyzed to form oxidized products, i.e., NO(2)(-) and NO(3)(-), and reveals a key reactive species produced during the photolysis of NDMA. Under acidic conditions, NO(2)(-) formed from the photodecomposition of NDMA was more prevalent than NO(3)(-). In this result, key species for the formation of NO(2)(-) are presumably N(2)O(3) and N(2)O(4) as termination products as well as NO and O(2) as reactants. Conversely, under alkaline conditions, NO(3)(-) was more prevalent than NO(2)(-). For this result, a key species for NO(3)(-) formation is presumably peroxynitrite (ONOO(-)). A detailed mechanistic study was performed with a competition reaction (or kinetics) between NDMA and p-nitrosodimethylaniline (PNDA) probe for hydroxyl radical (OH). It is fortuitous that the second-order rate constant for NDMA with an unknown reactive species (URS) was 5.13×10(8) M(-1) s(-1), which was similar to its published value for the reaction of NDMA+OH. Our study results showed that a key reactive species generated during NDMA photo-decomposition had hydroxyl radical-like reactivity and in particular, under alkaline conditions, it is most likely ONOO(-) as a source of nitrate ion. Therefore, for the first time, we experimentally report that an URS having OH-like reactivity can be formed during photochemical NDMA decomposition. This URS could contribute to the formations of NO(2)(-) and NO(3)(-). Copyright © 2012 Elsevier B.V. All rights reserved.

Surface complexation modeling of U(VI) adsorption by aquifer sediments from a former mill tailings site at Rifle, Colorado

USGS Publications Warehouse

Hyun, S.P.; Fox, P.M.; Davis, J.A.; Campbell, K.M.; Hayes, K.F.; Long, P.E.

2009-01-01

A study of U(VI) adsorption by aquifer sediment samples from a former uranium mill tailings site at Rifle, Colorado, was conducted under oxic conditions as a function of pH, U(VI), Ca, and dissolved carbonate concentration. Batch adsorption experiments were performed using <2mm size sediment fractions, a sand-sized fraction, and artificial groundwater solutions prepared to simulate the field groundwater composition. To encompass the geochemical conditions of the alluvial aquifer at the site, the experimental conditions ranged from 6.8 ?? 10-8 to 10-5 M in [U(VI)]tot, 7.2 to 8.0 in pH, 3.0 ?? 10-3 to 6.0 ?? 10 -3 M in [Ca2+], and 0.05 to 2.6% in partial pressure of carbon dioxide. Surface area normalized U(VI) adsorption Kd values for the sand and <2 mm sediment fraction were similar, suggesting a similar reactive surface coating on both fractions. A two-site two-reaction, nonelectrostatic generalized composite surface complexation model was developed and successfully simulated the U(VI) adsorption data. The model successfully predicted U(VI) adsorption observed from a multilevel sampling well installed at the site. A comparison of the model with the one developed previously for a uranium mill tailings site at Naturita, Colorado, indicated that possible calcite nonequilibrium of dissolved calcium concentration should be evaluated. The modeling results also illustrate the importance of the range of data used in deriving the best fit model parameters. ?? 2009 American Chemical Society.

[Adsorption of heavy metals on the surface of birnessite relationship with its Mn average oxidation state and adsorption sites].

PubMed

Wang, Yan; Tan, Wen-Feng; Feng, Xiong-Han; Qiu, Guo-Hong; Liu, Fan

2011-10-01

Adsorption characteristics of mineral surface for heavy metal ions are largely determined by the type and amount of surface adsorption sites. However, the effects of substructure variance in manganese oxide on the adsorption sites and adsorption characteristics remain unclear. Adsorption experiments and powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) were combined to examine the adsorption characteristics of Pb2+, Cu2+, Zn2+ and Cd2+ sequestration by birnessites with different Mn average oxidation state (AOS), and the Mn AOS dependent adsorption sites and adsorption characteristics. The results show that the maximum adsorption capacity of Pb2+, Cu2+, Zn2+ and Cd2+ increased with increasing birnessite Mn AOS. The adsorption capacity followed the order of Pb2+ > Cu2+ > Zn2+ > Cd2+. The observations suggest that there exist two sites on the surface of birnessite, i. e., high-binding-energy site (HBE site) and low-binding-energy site (LBE site). With the increase of Mn AOS for birnessites, the amount of HBE sites for heavy metal ions adsorption remarkably increased. On the other hand, variation in the amount of LBE sites was insignificant. The amount of LBE sites is much more than those of HBE sites on the surface of birnessite with low Mn AOS. Nevertheless, both amounts on the surface of birnessite with high Mn AOS are very close to each other. Therefore, the heavy metal ions adsorption capacity on birnessite is largely determined by the amount of HBE sites. On birnessite surface, adsorption of Cu2+, Zn2+, and Cd2+ mostly occurred at HBE sites. In comparison with Zn2+ and Cd2+, more Cu2+ adsorbed on the LBW sites. Pb2+ adsorption maybe occupy at both LBE sites and HBE sites simultaneously.

Liquid-Phase Adsorption Fundamentals.

ERIC Educational Resources Information Center

Cooney, David O.

1987-01-01

Describes an experiment developed and used in the unit operations laboratory course at the University of Wyoming. Involves the liquid-phase adsorption of an organic compound from aqueous solution on activated carbon, and is relevant to adsorption processes in general. (TW)

Adsorption of ion pairs onto graphene flakes and impacts of counterions during the adsorption processes

NASA Astrophysics Data System (ADS)

Zhu, Chang; Yun, Jiena; Wang, Qian; Yang, Gang

2018-03-01

Although cations and anions are two integral constituents for all electrolytes, adsorption of ion pairs onto carbonaceous materials gains obviously less attention than adsorption of only cations or anions. Here DFT calculations are employed finding that four adsorption configurations emerge for KI onto graphene flakes (GF) instead of three for the other ion pairs. Reservation of ionic bonds is critical to their stabilities, and the bilateral configurations, where GFs couple with both cations and anions, are disfavored due to rupture of ionic bonds. Relative stabilities of two vertical configurations can be regulated and even reversed through edge-functionalization. Surprisingly, the horizontal adsorption configurations, which are global energy minima as long as present, are non-existent for a majority of ion pairs, and their existence or not is determined by the adsorption differences between halide ions and alkali ions (△Ead). Counterions effects for both cations and anions increase with the atomic electronegativities and cations correspond to stronger counterion effects; e.g., Li+ added on the other side of GFs promotes the adsorption of F- more pronouncedly than edge-functionalization. Mechanisms of electron transfers are also discussed, and three alteration patterns by counterions are observed for each type of adsorption configurations. Furthermore, addition of counterions causes band gaps to vary within a wider range that may be useful to design electronic devices.

Surface complexation modeling of Cu(II) adsorption on mixtures of hydrous ferric oxide and kaolinite

PubMed Central

Lund, Tracy J; Koretsky, Carla M; Landry, Christopher J; Schaller, Melinda S; Das, Soumya

2008-01-01

Background The application of surface complexation models (SCMs) to natural sediments and soils is hindered by a lack of consistent models and data for large suites of metals and minerals of interest. Furthermore, the surface complexation approach has mostly been developed and tested for single solid systems. Few studies have extended the SCM approach to systems containing multiple solids. Results Cu adsorption was measured on pure hydrous ferric oxide (HFO), pure kaolinite (from two sources) and in systems containing mixtures of HFO and kaolinite over a wide range of pH, ionic strength, sorbate/sorbent ratios and, for the mixed solid systems, using a range of kaolinite/HFO ratios. Cu adsorption data measured for the HFO and kaolinite systems was used to derive diffuse layer surface complexation models (DLMs) describing Cu adsorption. Cu adsorption on HFO is reasonably well described using a 1-site or 2-site DLM. Adsorption of Cu on kaolinite could be described using a simple 1-site DLM with formation of a monodentate Cu complex on a variable charge surface site. However, for consistency with models derived for weaker sorbing cations, a 2-site DLM with a variable charge and a permanent charge site was also developed. Conclusion Component additivity predictions of speciation in mixed mineral systems based on DLM parameters derived for the pure mineral systems were in good agreement with measured data. Discrepancies between the model predictions and measured data were similar to those observed for the calibrated pure mineral systems. The results suggest that quantifying specific interactions between HFO and kaolinite in speciation models may not be necessary. However, before the component additivity approach can be applied to natural sediments and soils, the effects of aging must be further studied and methods must be developed to estimate reactive surface areas of solid constituents in natural samples. PMID:18783619

Imaging mycobacterial growth and division with a fluorogenic probe.

PubMed

Hodges, Heather L; Brown, Robert A; Crooks, John A; Weibel, Douglas B; Kiessling, Laura L

2018-05-15

Control and manipulation of bacterial populations requires an understanding of the factors that govern growth, division, and antibiotic action. Fluorescent and chemically reactive small molecule probes of cell envelope components can visualize these processes and advance our knowledge of cell envelope biosynthesis (e.g., peptidoglycan production). Still, fundamental gaps remain in our understanding of the spatial and temporal dynamics of cell envelope assembly. Previously described reporters require steps that limit their use to static imaging. Probes that can be used for real-time imaging would advance our understanding of cell envelope construction. To this end, we synthesized a fluorogenic probe that enables continuous live cell imaging in mycobacteria and related genera. This probe reports on the mycolyltransferases that assemble the mycolic acid membrane. This peptidoglycan-anchored bilayer-like assembly functions to protect these cells from antibiotics and host defenses. Our probe, quencher-trehalose-fluorophore (QTF), is an analog of the natural mycolyltransferase substrate. Mycolyltransferases process QTF by diverting their normal transesterification activity to hydrolysis, a process that unleashes fluorescence. QTF enables high contrast continuous imaging and the visualization of mycolyltransferase activity in cells. QTF revealed that mycolyltransferase activity is augmented before cell division and localized to the septa and cell poles, especially at the old pole. This observed localization suggests that mycolyltransferases are components of extracellular cell envelope assemblies, in analogy to the intracellular divisomes and polar elongation complexes. We anticipate QTF can be exploited to detect and monitor mycobacteria in physiologically relevant environments.

Adsorption dynamics of methyl violet onto granulated mesoporous carbon: Facile synthesis and adsorption kinetics.

PubMed

Kim, Yohan; Bae, Jiyeol; Park, Hosik; Suh, Jeong-Kwon; You, Young-Woo; Choi, Heechul

2016-09-15

A new and facile one-step synthesis method for preparing granulated mesoporous carbon (GMC) with three-dimensional spherical mesoporous symmetry is prepared to remove large molecular weight organic compounds in aqueous phase. GMC is synthesized in a single step using as-synthesized mesoporous carbon particles and organic binders through a simple and economical synthesis approach involving a simultaneous calcination and carbonization process. Characterization results obtained from SEM, XRD, as well as surface and porosity analysis indicate that the synthesized GMC has similar physical properties to those of the powdered mesoporous carbon and maintains the Brunauer-Emmett-Teller (BET) surface area and pore volume because the new synthesis method prevents the collapse of the pores during the granulation process. Batch adsorption experiments revealed GMC showed a substantial adsorption capacity (202.8 mg/g) for the removal of methyl violet as a target large molecular contaminant in aqueous phase. The mechanisms and dynamics modeling of GMC adsorption were also fully examined, which revealed that surface diffusion was rate limiting step on adsorption process of GMC. Adsorption kinetics of GMC enables 3 times faster than that of granular activated carbon in terms of surface diffusion coefficient. This is the first study, to the best of our knowledge, to synthesize GMC as an adsorbent for water purification by using facile granulation method and to investigate the adsorption kinetics and characteristics of GMC. This study introduces a new and simple method for the synthesis of GMC and reveals its adsorption characteristics for large molecular compounds in a water treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Crystal Face Distributions and Surface Site Densities of Two Synthetic Goethites: Implications for Adsorption Capacities as a Function of Particle Size.

PubMed

Livi, Kenneth J T; Villalobos, Mario; Leary, Rowan; Varela, Maria; Barnard, Jon; Villacís-García, Milton; Zanella, Rodolfo; Goodridge, Anna; Midgley, Paul

2017-09-12

Two synthetic goethites of varying crystal size distributions were analyzed by BET, conventional TEM, cryo-TEM, atomic resolution STEM and HRTEM, and electron tomography in order to determine the effects of crystal size, shape, and atomic scale surface roughness on their adsorption capacities. The two samples were determined by BET to have very different site densities based on Cr VI adsorption experiments. Model specific surface areas generated from TEM observations showed that, based on size and shape, there should be little difference in their adsorption capacities. Electron tomography revealed that both samples crystallized with an asymmetric {101} tablet habit. STEM and HRTEM images showed a significant increase in atomic-scale surface roughness of the larger goethite. This difference in roughness was quantified based on measurements of relative abundances of crystal faces {101} and {201} for the two goethites, and a reactive surface site density was calculated for each goethite. Singly coordinated sites on face {210} are 2.5 more dense than on face {101}, and the larger goethite showed an average total of 36% {210} as compared to 14% for the smaller goethite. This difference explains the considerably larger adsorption capacitiy of the larger goethite vs the smaller sample and points toward the necessity of knowing the atomic scale surface structure in predicting mineral adsorption processes.

Adsorption--from theory to practice.

PubMed

Dabrowski, A

2001-10-08

Adsorption at various interfaces has concerned scientists since the beginning of this century. This phenomenon underlies a number of extremely important processes of utilitarian significance. The technological, environmental and biological importance of adsorption can never be in doubt. Its practical applications in industry and environmental protection are of paramount importance. The adsorption of substrates is the first stage in many catalytic processes. The methods for separation of mixtures on a laboratory and on an industrial scale are increasingly based on utilising the change in concentration of components at the interface. Moreover, such vital problems as purification of water, sewages, air and soil are involved here too. On the other hand, many areas in which technological innovation has covered adsorption phenomena have been expanded more through art and craft than through science. A basic understanding of the scientific principles is far behind; in part because the study of interfaces requires extremely careful experimentation if meaningful and reproducible results are to be obtained. In recent years, however, considerable effort has been increasingly directed toward closing the gap between theory and practice. Crucial progress in theoretical description of the adsorption has been achieved, mainly through the development of new theoretical approaches formulated on a molecular level, by means of computer simulation methods and owing to new techniques which examine surface layers or interfacial regions. Moreover, during the last 15 years new classes of solid adsorbents have been developed, such as activated carbon fibres and carbon molecular sieves, fullerenes and heterofullerenes, microporous glasses and nanoporous--both carbonaceous and inorganic--materials. Nanostructured solids are very popular in science and technology and have gained extreme interest due to their sorption, catalytic, magnetic, optical and thermal properties. Although the development

Breakage mechanics for granular materials in surface-reactive environments

NASA Astrophysics Data System (ADS)

Zhang, Yida; Buscarnera, Giuseppe

2018-03-01

It is known that the crushing behaviour of granular materials is sensitive to the state of the fluids occupying the pore space. Here, a thermomechanical theory is developed to link such macroscopic observations with the physico-chemical processes operating at the microcracks of individual grains. The theory relies on the hypothesis that subcritical fracture propagation at intra-particle scale is the controlling mechanism for the rate-dependent, water-sensitive compression of granular specimens. First, the fracture of uniaxially compressed particles in surface-reactive environments is studied in light of irreversible thermodynamics. Such analysis recovers the Gibbs adsorption isotherm as a central component linking the reduction of the fracture toughness of a solid to the increase of vapour concentration. The same methodology is then extended to assemblies immersed in wet air, for which solid-fluid interfaces have been treated as a separate phase. It is shown that this choice brings the solid surface energy into the dissipation equations of the granular matrix, thus providing a pathway to (i) integrate the Gibbs isotherm with the continuum description of particle assemblies and (ii) reproduce the reduction of their yield strength in presence of high relative humidity. The rate-effects involved in the propagation of cracks and the evolution of breakage have been recovered by considering non-homogenous dissipation potentials associated with the creation of surface area at both scales. It is shown that the proposed model captures satisfactorily the compression response of different types of granular materials subjected to varying relative humidity. This result was achieved simply by using parameters based on the actual adsorption characteristics of the constituting minerals. The theory therefore provides a physically sound and thermodynamically consistent framework to study the behaviour of granular solids in surface-reactive environments.

Implementation Of Palladized Iron-Impregnated Reactive Activated Carbon (RAC) System For PCBs Cleanup: Effects Of PCB Loading, Reaction pH, And Co-Existing NOM And Ionic Species

EPA Science Inventory

For the treatment of chlorinated organic compounds in the environment, such as polychlorinated biphenyls (PCBs), we have developed reactive activated carbon (RAC) impregnated with Fe/Pd bimetallic nanoparticles. The RAC system can couple adsorption of PCBs to activated carbon wi...

Adsorption of octylamine on titanium dioxide

NASA Astrophysics Data System (ADS)

Siwińska, Daria; Kołodziejczak-Radzimska, Agnieszka; Krysztafkiewicz, Andrzej; Jesionowski, Teofil

2009-05-01

Processes of adsorption and desorption of a model active substance (octylamine) on the surface of unmodified titanium dioxide (E 171) have been performed. The effects of concentration of octylamine and time of the process on the character of adsorption have been studied and the efficiency of the adsorption/desorption has been determined. The samples obtained have been studied by X-ray diffraction. The nitrogen adsorption/desorption isotherms, particle size distribution and absorption capacities of water, dibutyl phthalate and paraffin oil have been determined. The efficiency of octylamine adsorption on the surface of the titanium dioxide has been found positively correlated with the concentration of octylamine in the initial solution. The desorption of octylamine has decreased with increasing concentration of this compound adsorbed. For octylamine in low concentrations the physical adsorption has been found to dominate, which is desirable when using TiO 2 in the production of pharmaceuticals.

Simultaneous leaching of arsenite, arsenate, selenite and selenate, and their migration in tunnel-excavated sedimentary rocks: II. Kinetic and reactive transport modeling.

PubMed

Tabelin, Carlito Baltazar; Sasaki, Ryosuke; Igarashi, Toshifumi; Park, Ilhwan; Tamoto, Shuichi; Arima, Takahiko; Ito, Mayumi; Hiroyoshi, Naoki

2017-12-01

Predicting the fates of arsenic (As) and selenium (Se) in natural geologic media like rocks and soils necessitates the understanding of how their various oxyanionic species behave and migrate under dynamic conditions. In this study, geochemical factors and processes crucial in the leaching and transport of arsenite (As III ), arsenate (As V ), selenite (Se IV ) and selenate (Se VI ) in tunnel-excavated rocks of marine origin were investigated using microscopic/extraction techniques, column experiments, dissolution-precipitation kinetics and one-dimensional reactive transport modeling. The results showed that evaporite salts were important because aside from containing As and Se, they played crucial roles in the evolution of pH and concentrations of coexisting ions, both of which had strong effects on adsorption-desorption reactions of As and Se species with iron oxyhydroxide minerals/phases. The observed leaching trends of As V , As III , Se IV and Se VI were satisfactorily simulated by one-dimensional reactive transport models, which predict that preferential adsorptions of As V and Se IV were magnified by geochemical changes in the columns due to water flow. Moreover, our results showed that migrations of As III , Se IV and Se VI could be predicted adequately by 1D solute transport with simple activity-K' d approach, but surface complexation was more reliable to simulate adsorption-desorption behavior of As V . Copyright © 2017 Elsevier Ltd. All rights reserved.

A comparative analysis of the cryo-compression and cryo-adsorption hydrogen storage methods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petitpas, G; Benard, P; Klebanoff, L E

2014-07-01

While conventional low-pressure LH₂ dewars have existed for decades, advanced methods of cryogenic hydrogen storage have recently been developed. These advanced methods are cryo-compression and cryo-adsorption hydrogen storage, which operate best in the temperature range 30–100 K. We present a comparative analysis of both approaches for cryogenic hydrogen storage, examining how pressure and/or sorbent materials are used to effectively increase onboard H₂ density and dormancy. We start by reviewing some basic aspects of LH₂ properties and conventional means of storing it. From there we describe the cryo-compression and cryo-adsorption hydrogen storage methods, and then explore the relationship between them, clarifyingmore » the materials science and physics of the two approaches in trying to solve the same hydrogen storage task (~5–8 kg H₂, typical of light duty vehicles). Assuming that the balance of plant and the available volume for the storage system in the vehicle are identical for both approaches, the comparison focuses on how the respective storage capacities, vessel weight and dormancy vary as a function of temperature, pressure and type of cryo-adsorption material (especially, powder MOF-5 and MIL-101). By performing a comparative analysis, we clarify the science of each approach individually, identify the regimes where the attributes of each can be maximized, elucidate the properties of these systems during refueling, and probe the possible benefits of a combined “hybrid” system with both cryo-adsorption and cryo-compression phenomena operating at the same time. In addition the relationships found between onboard H₂ capacity, pressure vessel and/or sorbent mass and dormancy as a function of rated pressure, type of sorbent material and fueling conditions are useful as general designing guidelines in future engineering efforts using these two hydrogen storage approaches.« less

Improving TCO-Conjugated Antibody Reactivity for Bioorthogonal Pretargeting

NASA Astrophysics Data System (ADS)

Chu, Tina Tingyi

Cancer remains a major cause of death because of its unpredictable progression. Utilizing bioorthogonal chemistry between trans-cyclooctene (TCO) and tetrazine to target imaging agents to tumors in two subsequent steps offers a more versatile platform for molecular imaging. This is accomplished by pretargeting TCO-modified primary antibody to cell surface biomarkers, followed by delivery of tetrazine-modified imaging probes. In previous work, it has been established that TCO-tetrazine chemistry can be applied to in vivo imaging, resulting in precise tumor detection. However, most TCO modifications on an antibody are not reactive because they are buried within hydrophobic domains. To expose and improve the reactivity, Rahim et al. incorporated a polyethylene glycol (PEG) linker through a two-step reaction with DBCO-azide, which successfully maintained 100% TCO functionality. In this project, various types of linkers were studied to improve the reactivity in a single step. Three primary types of linkers were studied: hydrophilic PEG chains, hydrophobic short linkers, and amphiphilic linkers. Our results show that PEG chain alone can only maintain 40% TCO reactivity. Unexpectedly, a short alkyl chain (valeric acid) provided superior results, with 60% TCO reactivity. Lengthening the alkyl chain did not improve results further. Finally, an amphiphilic linker containing valeric acid and PEG performed worse than either linker type alone, at ˜30% functionality. We conclude that our previous 100% functional TCO result obtained with the two-step coupling may have stemmed from generation of the DBCO/azide cycloaddition product. Future work will explore factors such as rigidity of linker structure, polarity, or charges.

Anisotropic nanocolloids: self-assembly, interfacial adsorption, and electrostatic screening

NASA Astrophysics Data System (ADS)

de Graaf, J.

2012-06-01

In this thesis we consider the influence of anisotropy on the behaviour of colloids using theory and simulations. The recent increase in the ability to synthesize anisotropic particles (cubes, caps, octapods, etc.) has led to samples of sufficient quality to perform self-assembly experiments. Our investigation is therefore particularly relevant to current and future experimental studies of colloids. We examine several topics for which shape anisotropy plays an important role: (1.) - Interfacial adsorption. We introduced the triangular-tessellation technique to approximate the surface areas and line length which are associated with a plane-particle intersection. Our method allowed us to determine the free energy of adsorption for a single irregular colloid with heterogeneous surface properties adsorbed at a flat liquid-liquid interface in the Pieranski approximation. Ellipsoids only adsorbed at the interface perpendicular to the interfacial normal. However, for cylinders we could find a metastable adsorption minimum corresponding to parallel adsorption. We also considered the possible time dependence of the adsorption process using simple dynamics. Finally, we studied the adsorption of truncated nanocubes with a contact-angle surface pattern and we observed that there are three prototypical equilibrium adsorption configurations for these particles. (2.) - Crystal-structure prediction. We extended an existing crystal-structure-prediction algorithm to predict structures for systems comprised of irregular hard particles. Using this technique we examined the high-density crystal structures for 17 irregular nonconvex shapes and we confirmed several mathematical conjectures for the packings of a large set of 142 convex polyhedra. We also proved that we have obtained the densest configurations for rhombicuboctahedra and rhombic enneacontrahedra, respectively. Moreover, we considered a family of truncated cubes, which interpolates between a cube and an octahedron, for which

Dimethyl diallyl ammonium chloride and diallylamin Co-polymer modified bio-film derived from palm dates for the adsorption of dyes.

PubMed

Jabli, Mahjoub; Saleh, Tawfik A; Sebeia, Nouha; Tka, Najeh; Khiari, Ramzi

2017-10-31

For the first time, co-polymer of dimethyl diallyl ammonium chloride and diallylamin (PDDACD) was used to modify the films derived from the waste of palm date fruits, which were then investigated by the purification of colored aqueous solutions. The physico-chemical characteristics were identified using data color, FT-IR spectroscopy, and SEM features. The modified films were evaluated as adsorbents of Methylene Blue (MB), Direct Yellow 50 (DY50), Reactive Blue 198 (RB198) and Naphtol Blue Black (NBB). High retention capacities were achieved in the following order: The equilibrium da DY50 (14 mg g -1 ) < RB198 (16 mg g -1 ) < NBB (63.9 mg g -1 ) < MB (150 mg g -1 ). The kinetic modeling of the data revealed that the adsorption data follows the pseudo second order model. It was fitted to the Langmuir, Freundlich, Temkin, and Dubinin-Redushkevich equations, and the data best fit the Freundlich model indicating that the adsorption might occur in the heterogeneous adsorption sites. These results reveal that PDDACD modified films are valuable materials for the treatment of industrial wastewater. Moreover, the as-prepared adsorbent is economically viable and easily controllable for pollutant adsorption.

Detection of irradiation induced reactive oxygen species production in live cells

NASA Astrophysics Data System (ADS)

Gao, Bo; Zhu, Debin

2006-09-01

Reactive oxygen species (ROS) is thought to play an important role in cell signaling of apoptosis, necrosis, and proliferation. Light irradiation increases mitochondrial reactive oxygen species (ROS) production and mediates its intracellular signaling by adjusting the redox potential in tumor cells. Mitochondria are the main source of ROS in the living cell. Superoxide anions (0 II - are likely the first ROS generated in the mitochondria following radiation damage, and then convert to hydrogen peroxide (H II0 II), hydroxyl radical (•OH), and singlet oxygen (10 II), etc. Conventional methods for research ROS production in mitochondria mostly use isolated mitochondria rather than mitochondria in living cells. In this study, a highly selective probe to detect mitochondrial 0 II - in live cells, MitoSOX TM Red, was applied to quantify the mitochondrial ROS production in human lung adenocarcinoma cells (ASTC-a-1) with laser scanning microscope (LSM) after ultraviolet C (UVC) and He-Ne laser irradiation. Dichiorodihydrofluoresein diacetate (DCFHDA), a common used fluorescent probe for ROS detection without specificity, were used as a comparison to image the ROS production. The fluorescent image of MItoSOX TM Red counterstained with MitoTracker Deep Red 633, a mitochondria selective probe, shows that the mitochondrial ROS production increases distinctly after UVC and He-Ne laser irradiation. DCFH-DA diffuses labeling throughout the cell though its fluorescence increases markedly too. In conclusion, the fluorescent method with MitoSOX TM Red reagent is proved to be a promising technique to research the role of ROS in radiation induced apoptosis.

[Treatment of organic waste gas by adsorption rotor].

PubMed

Zhu, Run-Ye; Zheng, Liang-Wei; Mao, Yu-Bo; Wang, Jia-De

2013-12-01

The adsorption rotor is applicable to treating organic waste gases with low concentration and high air volume. The performance of adsorption rotor for purifying organic waste gases was investigated in this paper. Toluene was selected as the simulative gaseous pollutant and the adsorption rotor was packed with honeycomb modified 13X molecular sieves (M-13X). Experimental results of the fixed adsorption and the rotor adsorption were analyzed and compared. The results indicated that some information on the fixed adsorption was useful for the rotor adsorption. Integrating the characteristics of the adsorbents, waste gases and the structures of the rotor adsorption, the formulas on optimal rotor speed and cycle removal efficiency of the adsorption rotor were deduced, based on the mass and heat balances of the adsorbing process. The numerical results were in good agreement with the experimental data, which meant that the formulas on optimal rotor speed and cycle removal efficiency could be effectively applied in design and operation of the adsorption rotor.

Tailoring the Adsorption and Reaction Chemistry of the Metal-Organic Frameworks UiO-66, UiO-66-NH2, and HKUST-1 via the Incorporation of Molecular Guests.

PubMed

Ploskonka, Ann M; DeCoste, Jared B

2017-06-28

Metal-organic frameworks (MOFs) are versatile materials highly regarded for their porous nature. Depending on the synthetic method, various guest molecules may remain in the pores or can be systematically loaded for various reasons. Herein, we present a study that explores the effect of guest molecules on the adsorption and reactivity of the MOF in both the gas phase and solution. The differences between guest molecule interactions and the subsequent effects on their activity are described for each system. Interestingly, different effects are observed and described in detail for each class of guest molecules studied. We determine that there is a strong effect of alcohols with the secondary building unit of UiO MOFs, while Lewis bases have an effect on the reactivity of the -NH 2 group in UiO-66-NH 2 and adsorption by the coordinatively unsaturated copper sites in HKUST-1. These effects must be considered when determining synthesis and activation methods of MOFs toward various applications.

Adsorption and co-adsorption of diclofenac and Cu(II) on calcareous soils.

PubMed

Graouer-Bacart, Mareen; Sayen, Stéphanie; Guillon, Emmanuel

2016-02-01

Pharmaceuticals are emerging contaminants and their presence in different compartments of the environment has been detected in many countries. In this study, laboratory batch experiments were conducted to characterize the adsorption of diclofenac, a widely used non-steroidal anti-inflammatory drug, on six calcareous soils. The adsorption of diclofenac was relatively low, which may lead to a risk of groundwater contamination and plant uptake. A correlation between the soil-water distribution coefficient Kd and soil characteristics has been highlighted. Indeed, diclofenac adsorption as a function of soil organic matter content (% OM) and Rt=% CaCO3/% OM was successfully described through a simple empirical model, indicating the importance of considering the inhibiting effect of CaCO3 on OM retention properties for a better assessment of diclofenac fate in the specific case of calcareous soils. The simultaneous co-adsorption of diclofenac and copper - a ubiquitous pollutant in the environment - at the water/soil interface, was also investigated. It appeared quite unexpectedly that copper did not have a significant influence on diclofenac retention. Copyright © 2015 Elsevier Inc. All rights reserved.

A new hydroxynaphthyl benzothiazole derived fluorescent probe for highly selective and sensitive Cu2 + detection

NASA Astrophysics Data System (ADS)

Tang, Lijun; He, Ping; Zhong, Keli; Hou, Shuhua; Bian, Yanjiang

2016-12-01

A new reactive probe, 1-(benzo[d]thiazol-2-yl)naphthalen-2-yl-picolinate (BTNP), was designed and synthesized. BTNP acts as a highly selective probe to Cu2 + in DMSO/H2O (7/3, v/v, Tris-HCl 10 mM, pH = 7.4) solution based on Cu2 + catalyzed hydrolysis of the picolinate ester moiety in BTNP, which leads to the formation of an ESIPT active product with dual wavelength emission enhancement. The probe also possesses the advantages of simple synthesis, rapid response and high sensitivity. The pseudo-first-order reaction rate constant was calculated to be 0.205 min- 1. Moreover, application of BTNP to Cu2 + detection in living cells and real water samples was also explored.

An overview of permeable reactive barriers for in situ sustainable groundwater remediation.

PubMed

Obiri-Nyarko, Franklin; Grajales-Mesa, S Johana; Malina, Grzegorz

2014-09-01

Permeable reactive barriers (PRBs) are one of the innovative technologies widely accepted as an alternative to the 'pump and treat' (P&T) for sustainable in situ remediation of contaminated groundwater. The concept of the technology involves the emplacement of a permeable barrier containing reactive materials across the flow path of the contaminated groundwater to intercept and treat the contaminants as the plume flows through it under the influence of the natural hydraulic gradient. Since the invention of PRBs in the early 1990s, a variety of materials has been employed to remove contaminants including heavy metals, chlorinated solvents, aromatic hydrocarbons, and pesticides. Contaminant removal is usually accomplished via processes such as adsorption, precipitation, denitrification and biodegradation. Despite wide acknowledgment, there are still unresolved issues about long term-performance of PRBs, which have somewhat affected their acceptability and full-scale implementation. The current paper presents an overview of the PRB technology, which includes the state of art, the merits and limitations, the reactive media used so far, and the mechanisms employed to transform or immobilize contaminants. The paper also looks at the design, construction and the long-term performance of PRBs. Copyright © 2014 Elsevier Ltd. All rights reserved.

NEURAL SUBSTRATES OF CUE-REACTIVITY: ASSOCIATION WITH TREATMENT OUTCOMES AND RELAPSE

PubMed Central

Courtney, Kelly E.; Schacht, Joseph P.; Hutchison, Kent; Roche, Daniel J.O.; Ray, Lara A.

2016-01-01

Given the strong evidence for neurological alterations at the basis of drug dependence, functional magnetic resonance imaging (fMRI) represents an important tool in the clinical neuroscience of addiction. fMRI cue-reactivity paradigms represent an ideal platform to probe the involvement of neurobiological pathways subserving the reward/motivation system in addiction and potentially offer a translational mechanism by which interventions and behavioral predictions can be tested. Thus, this review summarizes the research that has applied fMRI cue-reactivity paradigms to the study of adult substance use disorder treatment responses. Studies utilizing fMRI cue-reactivity paradigms for the prediction of relapse, and as a means to investigate psychosocial and pharmacological treatment effects on cue-elicited brain activation are presented within four primary categories of substances: alcohol, nicotine, cocaine, and opioids. Lastly, suggestions for how to leverage fMRI technology to advance addiction science and treatment development are provided. PMID:26435524

Fluorescent Probes Used for Detection of Hydrogen Peroxide under Biological Conditions.

PubMed

Żamojć, Krzysztof; Zdrowowicz, Magdalena; Jacewicz, Dagmara; Wyrzykowski, Dariusz; Chmurzyński, Lech

2016-05-03

Hydrogen peroxide is a well-established precursor of reactive oxygen and nitrogen species that are known to contribute to oxidative stress-the crucial factor responsible for the course of a wide range of phy-sicochemical processes as well as the genesis of various diseases, such as cancer and neurodegenerative disorders. Thus, the development of sensitive and selective methods for the detection and quantitative determination of hydrogen peroxide is of great importance in monitoring the in vivo production of that species and elucidating its biological functions. This review highlights the progress that has been made in the development of fluorescent and luminescent probes (excluding nanoparticles) employed to monitor hydrogen peroxide under biological conditions. Attention was focused on probes developed in the past 10 years.

Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cuadrado-Collados, Carlos; Fernández-Català, Javier; Fauth, François

For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N 2 with a total BET surface area of around 380 m 2 g -1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I)more » structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO 2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.« less

Understanding the breathing phenomena in nano-ZIF-7 upon gas adsorption

DOE PAGES

Cuadrado-Collados, Carlos; Fernández-Català, Javier; Fauth, François; ...

2017-09-11

For this research, synchrotron X-ray diffraction and inelastic neutron scattering measurements have been applied to evaluate the breathing phenomena in small nanocrystals of ZIF-7 upon gas adsorption. The experimental results show that an extended solvent exchange process with methanol is crucial to get a solvent-free narrow pore structure. Under these conditions, nano-ZIF-7 is indeed able to adsorb N 2 with a total BET surface area of around 380 m 2 g -1, in close agreement with theoretical predictions. The breathing phenomenon upon nitrogen adsorption is accompanied by a phase-to-phase transition, from a narrow-pore (phase II) to a large-pore (phase I)more » structure and a suppression of the cooperative deformation of the framework involving mainly the flapping motion of the benzimidazolate (bIm) ligand with the 4- and 6-membered rings. Whereas nitrogen requires temperature and pressure conditions close to condensation (close to 1 bar and 77 K) to induce the breathing in ZIF-7, CO 2 can do it under milder conditions (at room temperature and low relative pressures). These results reflect that the nature of the adsorptive probe and the gas–framework interactions, rather than the molecular diameter and/or shape, play a crucial role in defining the pressure and temperature conditions required to induce the breathing. Lastly, the presence of two different cavities in ZIF-7 as suggested by theoretical predictions, one with a window diameter of below 0.4 nm (cavity A) and the other with a pore size of around 0.6 nm (cavity B), has been confirmed experimentally using immersion calorimetry.« less

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…

Complementarity in radiochemical and infrared spectroscopic characterization of electrode adsorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wieckowski, A.

1994-03-01

Radioactive labelling and infrared spectroscopy are frequently used as direct, in situ probes into the structure of the electrochemical solid/liquid interface. These techniques are compared, in a polemical fashion, in the context of a recent publication by Parry et al. (Langmuir 1993, 9, 1878) where the research potential of the former technique was not adequately depicted. It is shown that radiotracers can clearly differentiate between the surface and solution species, both neutrals and anions. In addition to the surface specificity, the radiotracers offer a quantitative determination of adsorbate surface concentrations, a feature not yet demonstrated with surface infrared spectroscopy inmore » electrochemistry. Therefore, these two techniques are complementary. Examples of the combined radiochemical and spectroscopic measurements of adsorption with equivalent (smooth) electrode surfaces are quoted. 11 refs., 2 figs.« less

Fe-based MOFs for efficient adsorption and degradation of acid orange 7 in aqueous solution via persulfate activation

NASA Astrophysics Data System (ADS)

Li, Xianghui; Guo, Weilin; Liu, Zhonghua; Wang, Ruiqin; Liu, Hua

2016-04-01

Fe-based metal-organic frameworks (MOFs) including MIL-101(Fe), MIL-100(Fe), MIL-53(Fe), and MIL-88B(Fe) prepared via a facile solvothermal process were introduced as both adsorbents and catalysts to generate powerful radicals from persulfate for acid orange 7 (AO7) removal in aqueous solution. Various catalysts were described and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and X-ray photoelectron spectra. Because of the high specific surface area of the materials, we studied the adsorption isotherms of the four MILs by the fitting of Langmuir adsorption isotherm. Meanwhile, the catalytic activities in persulfate oxidation system were investigated. The results showed that the sequence of the materials ability in the combination of adsorption and degradation was MIL-101(Fe) > MIL-100(Fe) > MIL-53(Fe) > MIL-88B(Fe), which had a close connection with the activity of metal ion in active site of the catalysts and their different cages in size. Moreover, the reactive species in MILs/persulfate system were identified as sulfate radicals and hydroxyl radicals. The reaction mechanism for persulfate activation over MILs was also studied.

Dendrimer probes for enhanced photostability and localization in fluorescence imaging.

PubMed

Kim, Younghoon; Kim, Sung Hoon; Tanyeri, Melikhan; Katzenellenbogen, John A; Schroeder, Charles M

2013-04-02

Recent advances in fluorescence microscopy have enabled high-resolution imaging and tracking of single proteins and biomolecules in cells. To achieve high spatial resolutions in the nanometer range, bright and photostable fluorescent probes are critically required. From this view, there is a strong need for development of advanced fluorescent probes with molecular-scale dimensions for fluorescence imaging. Polymer-based dendrimer nanoconjugates hold strong potential to serve as versatile fluorescent probes due to an intrinsic capacity for tailored spectral properties such as brightness and emission wavelength. In this work, we report a new, to our knowledge, class of molecular probes based on dye-conjugated dendrimers for fluorescence imaging and single-molecule fluorescence microscopy. We engineered fluorescent dendritic nanoprobes (FDNs) to contain multiple organic dyes and reactive groups for target-specific biomolecule labeling. The photophysical properties of dye-conjugated FDNs (Cy5-FDNs and Cy3-FDNs) were characterized using single-molecule fluorescence microscopy, which revealed greatly enhanced photostability, increased probe brightness, and improved localization precision in high-resolution fluorescence imaging compared to single organic dyes. As proof-of-principle demonstration, Cy5-FDNs were used to assay single-molecule nucleic acid hybridization and for immunofluorescence imaging of microtubules in cytoskeletal networks. In addition, Cy5-FDNs were used as reporter probes in a single-molecule protein pull-down assay to characterize antibody binding and target protein capture. In all cases, the photophysical properties of FDNs resulted in enhanced fluorescence imaging via improved brightness and/or photostability. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

The adsorption of NO, NH3, N2 on carbon surface: a density functional theory study.

PubMed

Wang, Jiayong; Yang, Mo; Deng, Debing; Qiu, Shuxia

2017-08-11

To explore the adsorption mechanism of NO, NH 3 , N 2 on a carbon surface, and the effect of basic and acidic functional groups, density functional theory was employed to investigate the interactions between these molecules and carbon surfaces. Molecular electrostatic potential, Mulliken population analyses, reduced density gradient, and Mayer bond order analyses were used to clarify the adsorption mechanism. The results indicate that van der Waals interactions are responsible for N 2 physisorption, and N 2 is the least likely to adsorb on a carbon surface. Modification of carbon materials to decorate basic or acidic functional groups could enhance the NH 3 physisorption because of hydrogen bonding or electrostatic interactions, however, NO physisorption on a carbon surface is poor. Zig-zag sites are more reactive than armchair sites when these gas molecules absorb on the edge sites of carbon surface. Graphical abstract NH 3 , N 2 , NO adsortion on carbon surface.

Dye removal from textile industrial effluents by adsorption on exfoliated graphite nanoplatelets: kinetic and equilibrium studies.

PubMed

Carvallho, Marilda N; da Silva, Karolyne S; Sales, Deivson C S; Freire, Eleonora M P L; Sobrinho, Maurício A M; Ghislandi, Marcos G

2016-01-01

The concept of physical adsorption was applied for the removal of direct and reactive blue textile dyes from industrial effluents. Commercial graphite nanoplatelets were used as substrate, and the quality of the material was characterized by atomic force and transmission electron microscopies. Dye/graphite nanoplatelets water solutions were prepared varying their pH and initial dye concentration. Exceptionally high values (beyond 100 mg/L) for adsorptive capacity of graphite nanoplatelets could be achieved without complicated chemical modifications, and equilibrium and kinetic experiments were performed. Our findings were compared with the state of the art, and compared with theoretical models. Agreement between them was satisfactory, and allowed us to propose novel considerations describing the interactions of the dyes and the graphene planar structure. The work highlights the important role of these interactions, which can govern the mobility of the dye molecules and the amount of layers that can be stacked on the graphite nanoplatelets surface.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15.

PubMed

Bui, Tung Xuan; Pham, Viet Hung; Le, Son Thanh; Choi, Heechul

2013-06-15

The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (logKow) and acidity (pKa)). Good log-log linear relationships between the adsorption (Kd) and pH-dependent octanol-water coefficients (Kow(pH)) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10-100μgL(-1)) and the presence of natural organic matter. Copyright © 2013 Elsevier B.V. All rights reserved.

Factors influencing antibiotics adsorption onto engineered adsorbents.

PubMed

Xia, Mingfang; Li, Aimin; Zhu, Zhaolian; Zhou, Qin; Yang, Weiben

2013-07-01

The study evaluated the adsorption of two antibiotics by four engineered adsorbents (hypercrosslinked resin MN-202, macroporous resin XAD-4, activated carbon F-400, and multi-walled carbon nanotubes (MWCNT)) from aqueous solutions. The dynamic results demonstrated the dominant influence of pore size in adsorption. The adsorption amounts of antibiotics on XAD-4 were attributed to the hydrophobic effect, whereas steric hindrance or micropore-filling played a main role in the adsorption of antibiotics by F-400 because of its high microporosity. Aside from F-400, similar patterns of pH-dependent adsorption were observed, implying the importance of antibiotic molecular forms to the adsorption process for adsorbents. Increasing the ionic concentration with CaC12 produced particular adsorption characteristics on MWCNT at pH 2.0 and F-400 at pH 8.0, which were attributed to the highly available contact surfaces and molecular sieving, respectively. Its hybrid characteristics incorporating a considerable portion of mesopores and micropores made hypercross linked MN-202 a superior antibiotic adsorbent with high adsorption capacity. Furthermore, the adsorption capacity of MWCNT on the basis of surface area was more advantageous than that of the other adsorbents because MWCNT has a much more compact molecular arrangement.

Adsorption energies and prefactor determination for CH3OH adsorption on graphite.

PubMed

Doronin, M; Bertin, M; Michaut, X; Philippe, L; Fillion, J-H

2015-08-28

In this paper, we have studied adsorption and thermal desorption of methanol CH3OH on graphite surface, with the specific aim to derive from experimental data quantitative parameters that govern the desorption, namely, adsorption energy Eads and prefactor ν of the Polanyi-Wigner law. In low coverage regime, these two values are interconnected and usually the experiments can be reproduced with any couple (Eads, ν), which makes intercomparison between studies difficult since the results depend on the extraction method. Here, we use a method for determining independently the average adsorption energy and a prefactor value that works over a large range of incident methanol coverage, from a limited set of desorption curves performed at different heating rates. In the low coverage regime the procedure is based on a first order kinetic law, and considers an adsorption energy distribution which is not expected to vary with the applied heating rate. In the case of CH3OH multilayers, Eads is determined as 430 meV with a prefactor of 5 × 10(14) s(-1). For CH3OH submonolayers on graphite, adsorption energy of 470 ± 30 meV and a prefactor of (8 ± 3) × 10(16) s(-1) have been found. These last values, which do not change between 0.09 ML and 1 ML initial coverage, suggest that the methanol molecules form island-like structure on the graphite even at low coverage.

Low energy positrons as probes of reconstructed semiconductor surfaces.

NASA Astrophysics Data System (ADS)

Fazleev, Nail G.; Weiss, Alex H.

2007-03-01

Positron probes of semiconductor surfaces that play a fundamental role in modern science and technology are capable to non-destructively provide information that is both unique to the probe and complimentary to that extracted using other more standard techniques. We discuss recent progress in studies of the reconstructed Si(100), Si(111), Ge(100), and Ge(111) surfaces, clean and exposed to hydrogen and oxygen, using a surface characterization technique, Positron-Annihilation-Induced Auger-Electron Spectroscopy (PAES). Experimental PAES results are analyzed by performing first-principles calculations of positron surface states and annihilation probabilities of surface-trapped positrons with relevant core electrons for the reconstructed surfaces, taking into account discrete lattice effects, the electronic reorganization due to bonding, and charge redistribution effects at the surface. Effects of the hydrogen and oxygen adsorption on semiconductor surfaces on localization of positron surface state wave functions and annihilation characteristics are also analyzed. Theoretical calculations confirm that PAES intensities, which are proportional to annihilation probabilities of the surface trapped positrons that results in a core hole, are sensitive to the crystal face, surface structure and elemental content of the semiconductors.

Probing dimensionality using a simplified 4-probe method.

PubMed

Kjeldby, Snorre B; Evenstad, Otto M; Cooil, Simon P; Wells, Justin W

2017-10-04

4-probe electrical measurements have been in existence for many decades. One of the most useful aspects of the 4-probe method is that it is not only possible to find the resistivity of a sample (independently of the contact resistances), but that it is also possible to probe the dimensionality of the sample. In theory, this is straightforward to achieve by measuring the 4-probe resistance as a function of probe separation. In practice, it is challenging to move all four probes with sufficient precision over the necessary range. Here, we present an alternative approach. We demonstrate that the dimensionality of the conductive path within a sample can be directly probed using a modified 4-probe method in which an unconventional geometry is exploited; three of the probes are rigidly fixed, and the position of only one probe is changed. This allows 2D and 3D (and other) contributions the to resistivity to be readily disentangled. The required experimental instrumentation can be vastly simplified relative to traditional variable spacing 4-probe instruments.

Effects of Dissolved Carbonate on Arsenate Adsorption and Surface Speciation at the Hematite-Water Interface

USGS Publications Warehouse

Arai, Y.; Sparks, D.L.; Davis, J.A.

2004-01-01

Effects of dissolved carbonate on arsenate [As(V)] reactivity and surface speciation at the hematite-water interface were studied as a function of pH and two different partial pressures of carbon dioxide gas [PCO2 = 10 -3.5 atm and ???0; CO2-free argon (Ar)] using adsorption kinetics, pseudo-equilibrium adsorption/titration experiments, extended X-ray absorption fine structure spectroscopic (EXAFS) analyses, and surface complexation modeling. Different adsorbed carbonate concentrations, due to the two different atmospheric systems, resulted in an enhanced and/or suppressed extent of As(V) adsorption. As(V) adsorption kinetics [4 g L -1, [As(V)]0 = 1.5 mM and / = 0.01 M NaCl] showed carbonate-enhanced As(V) uptake in the air-equilibrated systems at pH 4 and 6 and at pH 8 after 3 h of reaction. Suppressed As(V) adsorption was observed in the air-equilibrated system in the early stages of the reaction at pH 8. In the pseudo-equilibrium adsorption experiments [1 g L-1, [As(V)] 0 = 0.5 mM and / = 0.01 M NaCl], in which each pH value was held constant by a pH-stat apparatus, effects of dissolved carbonate on As(V) uptake were almost negligible at equilibrium, but titrant (0.1 M HCl) consumption was greater in the air-equilibrated systems (PCO2 = 10-3.5 atm)than in the CO2-free argon system at pH 4-7.75. The EXAFS analyses indicated that As(V) tetrahedral molecules were coordinated on iron octahedral via bidentate mononuclear (???2.8 A??) and bidentate binuclear (???3.3 A??) bonding at pH 4.5-8 and loading levels of 0.46-3.10 ??M m-2. Using the results of the pseudoequilibrium adsorption data and the XAS analyses, the pH-dependent As(V) adsorption under the PCO2 = 10-3.5 atm and the CO2-free argon system was modeled using surface complexation modeling, and the results are consistent with the formation of nonprotonated bidentate surface species at the hematite surfaces. The results also suggest that the acid titrant consumption was strongly affected by changes to

Probing long-range structural order in SnPc/Ag(111) by umklapp process assisted low-energy angle-resolved photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Jauernik, Stephan; Hein, Petra; Gurgel, Max; Falke, Julian; Bauer, Michael

2018-03-01

Laser-based angle-resolved photoelectron spectroscopy is performed on tin-phthalocyanine (SnPc) adsorbed on silver Ag(111). Upon adsorption of SnPc, strongly dispersing bands are observed which are identified as secondary Mahan cones formed by surface umklapp processes acting on photoelectrons from the silver substrate as they transit through the ordered adsorbate layer. We show that the photoemission data carry quantitative structural information on the adsorbate layer similar to what can be obtained from a conventional low-energy electron diffraction (LEED) study. More specifically, we compare photoemission data and LEED data probing an incommensurate-to-commensurate structural phase transition of the adsorbate layer. Based on our results we propose that Mahan-cone spectroscopy operated in a pump-probe configuration can be used in the future to probe structural dynamics at surfaces with a temporal resolution in the sub-100-fs regime.

Bovine and human insulin adsorption at lipid monolayers: a comparison

NASA Astrophysics Data System (ADS)

Mauri, Sergio; Pandey, Ravindra; Rzeznicka, Izabela; Lu, Hao; Bonn, Mischa; Weidner, Tobias

2015-07-01

Insulin is a widely used peptide in protein research and it is utilised as a model peptide to understand the mechanics of fibril formation, which is believed to be the cause of diseases such as Alzheimer and Creutzfeld-Jakob syndrome. Insulin has been used as a model system due to its biomedical relevance, small size and relatively simple tertiary structure. The adsorption of insu lin on a variety of surfaces has become the focus of numerous studies lately. These works have helped in elucidating the consequence of surface/protein hydrophilic/hydrophobic interaction in terms of protein refolding and aggregation. Unfortunately, such model surfaces differ significantly from physiological surfaces. Here we spectroscopically investigate the adsorption of insulin at lipid monolayers, to further our understanding of the interaction of insulin with biological surfaces. In particular we study the effect of minor mutations of insulin’s primary amino acid sequence on its interaction with 1,2-Dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) model lipid layers. We probe the structure of bovine and human insulin at the lipid/water interface using sum frequency generation spectroscopy (SFG). The SFG experiments are complemented with XPS analysis of Langmuir-Schaefer deposited lipid/insulin films. We find that bovine and human insulin, even though very similar in sequence, show a substantially different behavior when interacting with lipid films.

Synthesis and CO{sub 2} adsorption study of modified MOF-5 with multi-wall carbon nanotubes and expandable graphite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ullah, Sami, E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Bustam, M. A., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com; Shariff, A. M., E-mail: samichemist1@gmail.com, E-mail: azmibustam@petronas.com.my, E-mail: azmish@petronas.com.my, E-mail: lkhlfh@gmail.com, E-mail: hmurshid@gmail.com, E-mail: nadiariazz@gmail.com

2014-10-24

MOF-5 was synthesized by solvothermal method and its reactivation under anhydrous conditions. This research is conducted to investigate the effect of MOF-5 and MOF-5 modified with multi-wall carbon nanotubes (MWCNTs) and expandable graphite (EG) on the performance of CO{sub 2} adsorption. The synthesized MOFs were characterized using Field emission scanning electron microscopy (FESEM) for surface morphology, Thermogravimetric analysis (TGA) for thermal stability, X-ray diffraction (XRD) for crystals plane, Brunauer-Emmet-Teller (BET) for surface area and CO{sub 2} adsorption. The result had showed that the modified MOF-5 enhanced the CO{sub 2} adsorption compared to the pure MOF-5. The increment in the CO{submore » 2} uptake capacities of MOF materials was attributed to the decrease in the pore size and enhancement of micropore volume of MOF-5 by multi-walled carbon nanotube and EG incorporation. The BET surface area of the synthesized MOF-5@MWCNTs is more than MOF-5. The CO{sub 2} sorption capacities of MOF-5 and MOF-5@MWCNTs were observed to increase from 0.00008 to 0.00048 mol g-1 at 298 K and 1 bar. The modified MOF-5@MWCNTs resulted in the highest CO{sub 2} adsorption followed by the modified MOF-5@ EG and lastly, MOF-5.« less

Precise control of surface electrostatic forces on polymer brush layers with opposite charges for resistance to protein adsorption.

PubMed

Sakata, Sho; Inoue, Yuuki; Ishihara, Kazuhiko

2016-10-01

Various molecular interaction forces are generated during protein adsorption process on material surfaces. Thus, it is necessary to control them to suppress protein adsorption and the subsequent cell and tissue responses. A series of binary copolymer brush layers were prepared via surface-initiated atom transfer radical polymerization, by mixing the cationic monomer unit and anionic monomer unit randomly in various ratios. Surface characterization revealed that the constructed copolymer brush layers exhibited an uniform super-hydrophilic nature and different surface potentials. The strength of the electrostatic interaction forces operating on these mixed-charge copolymer brush surfaces was evaluated quantitatively using force-versus-distance (f-d) curve measurements by atomic force microscopy (AFM) and probes modified by negatively charged carboxyl groups or positively charged amino groups. The electrostatic interaction forces were determined based on the charge ratios of the copolymer brush layers. Notably, the surface containing equivalent cationic/anionic monomer units hardly interacted with both the charged groups. Furthermore, the protein adsorption force and the protein adsorption mass on these surfaces were examined by AFM f-d curve measurement and surface plasmon resonance measurement, respectively. To clarify the influence of the electrostatic interaction on the protein adsorption behavior on the surface, three kinds of proteins having negative, positive, and relatively neutral net charges under physiological conditions were used in this study. We quantitatively demonstrated that the amount of adsorbed proteins on the surfaces would have a strong correlation with the strength of surface-protein interaction forces, and that the strength of surface-protein interaction forces would be determined from the combination between the properties of the electrostatic interaction forces on the surfaces and the charge properties of the proteins. Especially, the

Isosteric heat of hydrogen adsorption on MOFs: comparison between adsorption calorimetry, sorption isosteric method, and analytical models

NASA Astrophysics Data System (ADS)

Kloutse, A. F.; Zacharia, R.; Cossement, D.; Chahine, R.; Balderas-Xicohténcatl, R.; Oh, H.; Streppel, B.; Schlichtenmayer, M.; Hirscher, M.

2015-12-01

Isosteric heat of adsorption is an important parameter required to describe the thermal performance of adsorptive storage systems. It is most frequently calculated from adsorption isotherms measured over wide ranges of pressure and temperature, using the so-called adsorption isosteric method. Direct quantitative estimation of isosteric heats on the other hand is possible using the coupled calorimetric-volumetric method, which involves simultaneous measurement of heat and adsorption. In this work, we compare the isosteric heats of hydrogen adsorption on microporous materials measured by both methods. Furthermore, the experimental data are compared with the isosteric heats obtained using the modified Dubinin-Astakhov, Tóth, and Unilan adsorption analytical models to establish the reliability and limitations of simpler methods and assumptions. To this end, we measure the hydrogen isosteric heats on five prototypical metal-organic frameworks: MOF-5, Cu-BTC, Fe-BTC, MIL-53, and MOF-177 using both experimental methods. For all MOFs, we find a very good agreement between the isosteric heats measured using the calorimetric and isosteric methods throughout the range of loading studied. Models' prediction on the other hand deviates from both experiments depending on the MOF studied and the range of loading. Under low-loadings of less than 5 mol kg-1, the isosteric heat of hydrogen adsorption decreases in the order Cu-BTC > MIL-53 > MOF-5 > Fe-BTC > MOF-177. The order of isosteric heats is coherent with the strength of hydrogen interaction revealed from previous thermal desorption spectroscopy measurements.

Influence of surface oxides on the adsorption of naphthalene onto multiwalled carbon nanotubes.

PubMed

Cho, Hyun-Hee; Smith, Billy A; Wnuk, Joshua D; Fairbrother, D Howard; Ball, William P

2008-04-15

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5.

PubMed

Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

2016-08-25

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example.

Adsorption Device Based on a Langatate Crystal Microbalance for High Temperature High Pressure Gas Adsorption in Zeolite H-ZSM-5

PubMed Central

Ding, Wenjin; Baracchini, Giulia; Klumpp, Michael; Schwieger, Wilhelm; Dittmeyer, Roland

2016-01-01

We present a high-temperature and high-pressure gas adsorption measurement device based on a high-frequency oscillating microbalance (5 MHz langatate crystal microbalance, LCM) and its use for gas adsorption measurements in zeolite H-ZSM-5. Prior to the adsorption measurements, zeolite H-ZSM-5 crystals were synthesized on the gold electrode in the center of the LCM, without covering the connection points of the gold electrodes to the oscillator, by the steam-assisted crystallization (SAC) method, so that the zeolite crystals remain attached to the oscillating microbalance while keeping good electroconductivity of the LCM during the adsorption measurements. Compared to a conventional quartz crystal microbalance (QCM) which is limited to temperatures below 80 °C, the LCM can realize the adsorption measurements in principle at temperatures as high as 200-300 °C (i.e., at or close to the reaction temperature of the target application of one-stage DME synthesis from the synthesis gas), owing to the absence of crystalline-phase transitions up to its melting point (1,470 °C). The system was applied to investigate the adsorption of CO2, H2O, methanol and dimethyl ether (DME), each in the gas phase, on zeolite H-ZSM-5 in the temperature and pressure range of 50-150 °C and 0-18 bar, respectively. The results showed that the adsorption isotherms of these gases in H-ZSM-5 can be well fitted by Langmuir-type adsorption isotherms. Furthermore, the determined adsorption parameters, i.e., adsorption capacities, adsorption enthalpies, and adsorption entropies, compare well to literature data. In this work, the results for CO2 are shown as an example. PMID:27585356

On the quantification of the dissolved hydroxyl radicals in the plasma-liquid system using the molecular probe method

NASA Astrophysics Data System (ADS)

Ma, Yupengxue; Gong, Xinning; He, Bangbang; Li, Xiaofei; Cao, Dianyu; Li, Junshuai; Xiong, Qing; Chen, Qiang; Chen, Bing Hui; Huo Liu, Qing

2018-04-01

Hydroxyl (OH) radical is one of the most important reactive species produced by plasma-liquid interactions, and the OH in liquid phase (dissolved OH radical, OHdis) takes effect in many plasma-based applications due to its high reactivity. Therefore, the quantification of the OHdis in a plasma-liquid system is of great importance, and a molecular probe method usually used for the OHdis detection might be applied. Herein, we investigate the validity of using the molecular probe method to estimate the [OHdis] in the plasma-liquid system. Dimethyl sulfoxide is used as the molecular probe to estimate the [OHdis] in an air plasma-liquid system, and usually the estimation of [OHdis] is deduced by quantifying the OHdis-induced derivative, the formaldehyde (HCHO). The analysis indicates that the true concentration of the OHdis should be estimated from the sum of three terms: the formed HCHO, the existing OH scavengers, and the H2O2 formed from the OHdis. The results show that the measured [HCHO] needs to be corrected since the HCHO consumption is not negligible in the plasma-liquid system. We conclude from the results and the analysis that the molecular probe method generally underestimates the [OHdis] in the plasma-liquid system. If one wants to obtain the true concentration of the OHdis in the plasma-liquid system, one needs to know the consumption behavior of the OHdis-induced derivatives, the information of the OH scavengers (such as hydrated electron, atomic hydrogen besides the molecular probe), and also the knowledge of the H2O2 formed from the OHdis.

Hg2+-reactive double hydrophilic block copolymer assemblies as novel multifunctional fluorescent probes with improved performance.

PubMed

Hu, Jinming; Li, Changhua; Liu, Shiyong

2010-01-19

We report on novel type of responsive double hydrophilic block copolymer (DHBC)-based multifunctional chemosensors to Hg(2+) ions, pH, and temperatures and investigate the effects of thermo-induced micellization on the detection sensitivity. Well-defined DHBCs bearing rhodamine B-based Hg(2+)-reactive moieties (RhBHA) in the thermo-responsive block, poly(ethylene oxide)-b-poly(N-isopropylacrylamide-co-RhBHA) (PEO-b-P(NIPAM-co-RhBHA)), were synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Nonfluorescent RhBHA moieties are subjected to selective ring-opening reaction upon addition of Hg(2+) ions or lowering solution pH, producing highly fluorescent acyclic species. Thus, at room temperature PEO-b-P(NIPAM-co-RhBHA) DHBCs can serve as water-soluble multifunctional and efficient fluorescent chemosensors to Hg(2+) ions and pH. Upon heating above the lower critical solution temperature (approximately 36 degrees C) of the PNIPAM block, they self-assemble into micelles possessing P(NIPAM-co-RhBHA) cores and well-solvated PEO coronas, which were fully characterized by dynamic and static laser light scattering. It was found that the detection sensitivity to Hg(2+) ions and pH could be dramatically improved at elevated temperatures due to fluorescence enhancement of RhBHA residues in the acyclic form, which were embedded within hydrophobic cores of thermo-induced micellar aggregates. This work represents a proof-of-concept example of responsive DHBC-based multifunctional fluorescent chemosensors for the highly efficient detection of Hg(2+) ions, pH, and temperatures with tunable detection sensitivity. Compared to reaction-based small molecule Hg(2+) probes in previous literature reports, the integration of stimuli-responsive block copolymers with well-developed small molecule-based selective sensing moieties in the current study are expected to exhibit preferred advantages including enhanced detection sensitivity, water dispersibility

DFT study on the adsorption behavior and electronic response of AlN nanotube and nanocage toward toxic halothane gas

NASA Astrophysics Data System (ADS)

Mohammadi, R.; Hosseinian, A.; Khosroshahi, E. Saedi; Edjlali, L.; Vessally, E.

2018-04-01

We have investigated the adsorption of a halothane molecule on the AlN nanotube, and nanocage using density functional theory calculations. We predicted that the halothane molecule tends to be physically adsorbed on the surface of AlN nanotube with adsorption energy (Ead) of -4.2 kcal/mol. The electronic properties of AlN nanotube are not affected by the halothane, and it is not a sensor. But the AlN nanocage is more reactive than the AlN nanotube because of its higher curvature. The halothane tends to be adsorbed on a hexagonal ring, an Alsbnd N bond, and a tetragonal ring of the AlN nanocage. The adsorption ability order is as follows: tetragonal ring (Ead = -14.7 kcal/mol) > Alsbnd N bond (Ead = -12.3 kcal/mol) > hexagonal ring (Ead = -10.1 kcal/mol). When a halothane molecule is adsorbed on the AlN nanocage, its electrical conductivity is increased, demonstrating that it can yield an electronic signal at the presence of this molecule, and can be employed in chemical sensors. The AlN nanocage benefits from a short recovery time of about 58 ms at room temperature.

Mechanism of p-substituted phenol oxidation at a Ti4O7 reactive electrochemical membrane.

PubMed

Zaky, Amr M; Chaplin, Brian P

2014-05-20

This research investigated the removal mechanisms of p-nitrophenol, p-methoxyphenol, and p-benzoquinone at a porous Ti4O7 reactive electrochemical membrane (REM) under anodic polarization. Cross-flow filtration experiments and density functional theory (DFT) calculations indicated that p-benzoquinone removal was primarily due to reaction with electrochemically formed OH(•), while the dominant removal mechanism of p-nitrophenol and p-methoxyphenol was a function of the anodic potential. At low anodic potentials (1.7-1.8 V/SHE), p-nitrophenol and p-methoxyphenol were removed primarily by an electrochemical adsorption/polymerization mechanism on the REM. Increasing anodic potentials (1.9-3.2 V/SHE) resulted in the electroassisted adsorption mechanism contributing far less to p-methoxyphenol removal compared to p-nitrophenol. DFT calculations indicated that an increase in anodic potential resulted in a shift in p-methoxyphenol removal from a 1e(-) direct electron transfer (DET) reaction that resulted in radical formation and significant adsorption/polymerization, to a 2e(-) DET reaction that formed nonadsorbing products (i.e., p-benzoquinone). However, the anodic potentials were too low for the 2e(-) DET reaction to be thermodynamically favorable for p-nitrophenol. The decreased COD adsorption for p-nitrophenol at higher anodic potentials was attributed to reaction of soluble/adsorbed organics with OH(•). These results provide the first mechanistic explanation for p-substituted phenolic compound removal during advanced electrochemical oxidation processes.

Mechanism of tyramine adsorption on Ca-montmorillonite.

PubMed

Chang, Po-Hsiang; Jiang, Wei-Teh; Li, Zhaohui

2018-06-10

Tyramine (TY) adsorption on a Ca-montmorillonite (SAz-2) was investigated with batch experiments and complementary analyses utilizing ultra-high performance liquid chromatography, ion chromatography, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and thermogravimetry (TG). The adsorption reached equilibrium in 8 h, complying with the pseudo-second-order rate equation, and came to an adsorption capacity of 682 mmol kg -1 at pH 6-8.1, utilizing the Langmuir isotherm model. The adsorption of TY and desorption of exchangeable cations exhibited a linear relationship with a slope of 0.9, implying that the adsorption was largely influenced by a cation exchange mechanism. The effective adsorption was further verified by the characteristic TY bands in the FTIR spectra and the signals of mass loss due to TY decomposition in the TG measurements of the clay after adsorption experiments. Intercalation of hydrated TY into the clay interlayer was confirmed by XRD and TG analyses of the heated samples loaded with TY. The adsorption reached only 0.57 cation exchange capacity of the clay which was probably limited by the low charge density of TY as compared to the negative charge density of the clay surface and by the steric effects arising from the hydration of TY that increased its molecular size. Adsorption of TY on montmorillonite can make TY more resistant to thermal decomposition and possibly better preserved in aquatic and soil environments. Copyright © 2018 Elsevier B.V. All rights reserved.

Tunable gas adsorption in graphene oxide framework

NASA Astrophysics Data System (ADS)

Razmkhah, Mohammad; Moosavi, Fatemeh; Taghi Hamed Mosavian, Mohammad; Ahmadpour, Ali

2018-06-01

Effect of length of linker inter-space was studied on the adsorption capacity of CO2 by graphene oxide framework (GOF). Effect of linker inter-space of 14, 11, and 8 Å was studied here. The linker inter-space of 11 Å showed the highest CO2 adsorption capacity. A dual-site Langmuir model was observed for adsorption of CO2 and CH4 into the GOF. According to radial distribution function (RDF), facial and central atoms of linker are the dual-site predicted by Langmuir model. Two distinguishable sites of adsorption and parallel orientation of CO2 are the main reasons of high adsorption capacity in 11 Å linker inter-space. Gas-adsorbent affinity obtains the orientation of CO2 near the linker. The affinity in the 11 Å linker inter-space is the highest. Thus, it forces the CO2 to lay parallel and orient more localized than the other GOFs. In addition, CH4 resulted higher working capacity than CO2 in 14 Å. This occurs because of the change in gas-adsorbent affinity by changing pressure. An entrance adsorption occurs out of the pore of the GOF. This adsorption is not as stable as deep adsorption.

Adsorption of cadmium(II) on waste biomaterial.

PubMed

Baláž, M; Bujňáková, Z; Baláž, P; Zorkovská, A; Danková, Z; Briančin, J

2015-09-15

Significant increase of the adsorption ability of the eggshell biomaterial toward cadmium was observed upon milling, as is evidenced by the value of maximum monolayer adsorption capacity of 329mgg(-1), which is markedly higher than in the case of most "green" sorbents. The main driving force of the adsorption was proven to be the presence of aragonite phase as a consequence of phase transformation from calcite occurring during milling. Cadmium is adsorbed in a non-reversible way, as documented by different techniques (desorption tests, XRD and EDX measurements). The optimum pH for cadmium adsorption was 7. The adsorption process was accompanied by the increase of the value of specific surface area. The course of adsorption has been described by Langmuir, Freundlich and Dubinin-Radushkevich isotherms. The adsorption kinetics was evaluated using three models, among which the best correlation coefficients and the best normalized standard deviation values were achieved for the pseudo-second order model and the intraparticle diffusion model, respectively. Copyright © 2015 Elsevier Inc. All rights reserved.

Design and preparation of quantum dots fluorescent probes for in situ identification of Microthrix parvicella in bulking sludge.

PubMed

Fei, Xuening; Sun, Wenke; Cao, Lingyun; Jiao, Xiumei; Lin, Dayong; Jia, Guozhi

2016-01-01

A series of quantum dots (QDs) fluorescent probes for the in situ identification of Microthrix parvicella (M. parvicella) in bulking sludge were designed and prepared. In the preparation of CdTe/CdS QDs, the 11-mercaptoundecanoic acid (11-acid) and 16-mercaptohexadecanoic acid (16-acid) were used as the stabilizer. The prepared QDs probes were characterized by Fourier transform infrared (FT-IR), X-ray diffraction (XRD), and transmission electron microscopy (TEM), and the results showed that the CdTe/CdS QDs formed a core-shell structure and the long carbon chain was successfully grafted onto its surface. And the three QDs probes had different crystallinity and particle size, which was due to the inhibition effect of long carbon chain. The optical properties test results showed that although the formed core-shell structure and long carbon chain affected the fluorescent intensity, adsorption, and emission spectra of the QDs probes, the probes B and C had a large stokes-shift of 82 and 101 nm, which was a benefit for their fluorescent labeling property. In the fluorescent identification of M. parvicella, the probes B and C effectively adsorbed onto the surface of M. parvicella through a hydrophobic bond, and then identified M. parvicella by their unique fluorescence. In addition, it was found that a better hydrophobic property resulted in better identification efficiency.

Gas adsorption capacity of wood pellets

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

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 (CO 2) uptake compared to the regular and torrefied pellets. The high CO 2 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 pelletsmore » 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 CO 2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO 2, 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

Adsorption of ferrous ions onto montmorillonites

NASA Astrophysics Data System (ADS)

Qin, Dawei; Niu, Xia; Qiao, Min; Liu, Gang; Li, Hongxin; Meng, Zhenxiao

2015-04-01

The adsorption of Fe (II) onto montmorillonites was investigated through initial concentration, contact time, pH and temperature. During the whole adsorption process, the ascorbic acid (Vitamin C) was added as a kind of antioxidant, at the same time, deionized water (after boiling) and nitrogen protection were also used to avoid oxidation. The Fe2+/Fetotal ratio of the iron exists in the Fe-montmorillonites was found more than 95%. Two kinetic models, including pseudo-first-order and pseudo-second-order model, were used to analyze the adsorption process of Fe (II) on montmorillonites. The results of our study showed that adsorption process fitted with pseudo-second-order well. Adsorption isotherms showed that Langmuir model was better than Freundlich model. The thermodynamic parameters ΔG0 and ΔH0 were 3.696 kJ/mol and 6.689 kJ/mol (we just gave the values at 298 K), respectively. The positive values at different temperatures showed that the adsorption process was non-spontaneous and endothermic. The characteristics of materials were determined by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Surface area and porosity analyzer, Thermogravimetric analysis (TGA), Differential scanning calorimeter (DSC) and Zeta potential distribution.

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 (CO 2) uptake compared to the regular and torrefied pellets. The high CO 2 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 pelletsmore » 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 CO 2 (7.24 kJ/mol), demonstrating the mechanism of chemical adsorption and physical adsorption for CO and CO 2, 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

Comparative evaluation of probing depth and clinical attachment level using a manual probe and Florida probe.

PubMed

Kour, Amandeep; Kumar, Ashish; Puri, Komal; Khatri, Manish; Bansal, Mansi; Gupta, Geeti

2016-01-01

To compare and evaluate the intra- and inter-examiner efficacy and reproducibility of the first-generation manual (Williams) probe and the third-generation Florida probe in terms of measuring pocket probing depth (PD) and clinical attachment level (CAL). Forty subjects/4000 sites were included in this comparative, cross-sectional study. Group- and site-wise categorizations were done. Based on gingival index, PD, and CAL, patients were divided into four groups, i.e., periodontally healthy, gingivitis, mild to moderate periodontitis, and severe periodontitis. Further, based on these parameters, a total of 4000 sites, with 1000 sites in each category randomly selected from these 40 patients, were taken. Full mouth PD and CAL measurements were recorded with two probes, by Examiner 1 and on Ramfjord teeth by Examiner 2. Full mouth and Ramfjord teeth group- and site-wise PD obtained with the manual probe by both the examiners were statistically significantly deeper than that obtained with the Florida probe. The full mouth and Ramfjord teeth mean CAL measurement by Florida probe was higher as compared to manual probe in mild to moderate periodontitis group and sites, whereas in severe periodontitis group and sites, manual probe recorded higher CAL as compared to Florida probe. Mean PD and CAL measurements were deeper with the manual probe as compared to the Florida probe in all the groups and sites, except for the mild-moderate periodontitis group and sites where the CAL measurements with the manual probe were less than the Florida probe. Manual probe was more reproducible and showed less interexaminer variability as compared to the Florida probe.

Adsorption of natural organic matter and disinfection byproduct precursors from surface water onto TiO2 nanoparticles: pH effects, isotherm modelling and implications for using TiO2 for drinking water treatment.

PubMed

Gora, Stephanie L; Andrews, Susan A

2017-05-01

Titanium dioxide is a photocatalyst that can remove organic contaminants of interest to the drinking water treatment industry, including natural organic matter (NOM) and disinfection byproduct (DBP) precursors. The photocatalytic reaction occurs in two steps: adsorption of the contaminant followed by degradation of the adsorbed contaminant upon irradiation with UV light. The second part of this process can lead to the formation of reactive intermediates and negative impacts on treated water quality, such as increased DBP formation potential (DBPfp). Adsorption alone does not result in the formation of reactive intermediates and thus may prove to be a safe way to incorporate TiO 2 into drinking water treatment processes. The goal of this study was to expand on the current understanding of NOM adsorption on TiO 2 and examine it in a drinking water context by observing NOM adsorption from real water sources and evaluating the effects of the resulting reductions on the DBPfp of the treated water. Bottle point isotherm tests were conducted with raw water from two Canadian water treatment plants adjusted to pH 4, pH 6 and pH 8 and dosed with TiO 2 nanoparticles. The DOC results were a good fit to a modified Freundlich isotherm. DBP precursors and liquid chromatography with organic carbon detection NOM fractions associated with DBP formation were removed to some extent at all pHs, but most effectively at pH 4. Copyright © 2017 Elsevier Ltd. All rights reserved.

Specificity tests of an oligonucleotide probe against food-outbreak salmonella for biosensor detection

NASA Astrophysics Data System (ADS)

Chen, I.-H.; Horikawa, S.; Xi, J.; Wikle, H. C.; Barbaree, J. M.; Chin, B. A.

2017-05-01

Phage based magneto-elastic (ME) biosensors have been shown to be able to rapidly detect Salmonella in various food systems to serve food pathogen monitoring purposes. In this ME biosensor platform, the free-standing strip-shaped magneto-elastic sensor is the transducer and the phage probe that recognizes Salmonella in food serves as the bio-recognition element. According to Sorokulova et al. at 2005, a developed oligonucleotide probe E2 was reported to have high specificity to Salmonella enterica Typhimurium. In the report, the specificity tests were focused in most of Enterobacterace groups outside of Salmonella family. Here, to understand the specificity of phage E2 to different Salmonella enterica serotypes within Salmonella Family, we further tested the specificity of the phage probe to thirty-two Salmonella serotypes that were present in the major foodborne outbreaks during the past ten years (according to Centers for Disease Control and Prevention). The tests were conducted through an Enzyme linked Immunosorbent Assay (ELISA) format. This assay can mimic probe immobilized conditions on the magnetoelastic biosensor platform and also enable to study the binding specificity of oligonucleotide probes toward different Salmonella while avoiding phage/ sensor lot variations. Test results confirmed that this oligonucleotide probe E2 was high specific to Salmonella Typhimurium cells but showed cross reactivity to Salmonella Tennessee and four other serotypes among the thirty-two tested Salmonella serotypes.

Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

PubMed

Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

2017-09-11

Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log K ow ), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

Water adsorption on surface-modified cellulose nanocrystals

NASA Astrophysics Data System (ADS)

Wei, Zonghui; Sinko, Robert; Keten, Sinan; Luijten, Erik

Cellulose nanocrystals (CNCs) have attracted much attention as a filler phase for polymer nanocomposites due to their impressive mechanical properties, low cost, and environmental sustainability. Despite their promise for this application, there are still numerous obstacles that prevent optimal performance of CNC-polymer nanocomposites, such as poor filler dispersion and high levels of water absorption. One way to mitigate these negative effects is to modify CNC surfaces. Computational approaches can be utilized to obtain direct insight into the properties of modified CNC surfaces and probe the interactions of CNCs with other materials to facilitate the experimental design of nanocomposites. We use atomistic grand-canonical Monte Carlo simulations to study how surface modification of ion-exchanged sulfated cellulose nanocrystals (Na-CNCs) impacts water adsorption. We find that methyl(triphenyl)phosphonium-exchanged CNCs adsorb less water than Na-CNCs at the same relative humidity, supporting recent experimental dynamic vapor sorption measurements. By characterizing the distribution and configuration of water molecules near the modified CNC surfaces we determine how surface modifications disrupt CNC-water interactions.

"Off-on" red-emitting fluorescent probes with large Stokes shifts for nitric oxide imaging in living cells.

PubMed

Chen, Jian-Bo; Zhang, Hui-Xian; Guo, Xiao-Feng; Wang, Hong; Zhang, Hua-Shan

2013-09-01

Fluorescent probes with larger Stokes shifts in the far-visible and near-infrared spectral region (600-900 nm) are more superior for cellular imaging and biological analysis due to avoiding light scattering interference, reducing autofluorescence from biological sample and encouraging deeper tissue penetration in vivo imaging. In this work, two bis-methoxyphenyl-BODIPY fluorescent probes for the detection of nitric oxide (NO) have been firstly synthesized. Under physiological conditions, these probes can react with NO to form the corresponding triazoles with 250- and 70-fold turn-on fluorescence emitting at 590 and 620 nm, respectively. Moreover, the triazole forms of these probes have large Stokes shifts of 38 nm, in contrast to 10 nm of existing BODIPY probes for NO. Excellent selectivity has been observed against other reactive oxygen/nitrogen species, ascorbic acid and biological matrix. After the evaluation of MTT assay, new fluorescent probes have been successfully applied to fluorescence imaging of NO released from RAW 264.7 macrophages by co-stimulation of lipopolysaccharide and interferon-γ. The experimental results indicate that our fluorescent probes can be powerful candidates for fluorescence imaging of NO due to the low background interference and high detection sensitivity.

Adsorption of goethite onto quartz and kaolinite

USGS Publications Warehouse

Goldberg, M.C.; Weiner, Eugene R.; Boymel, P.M.

1984-01-01

The adsorption of colloidal goethite onto quartz and kaolinite substrates has been studied as a function of pH and NaCl concentration. Goethite adsorption was measured quantitatively by Fourier-transform infrared spectroscopy. The results indicate that adsorption onto both substrates is due primarily to coulombic forces; however, the pH dependence of adsorption is very different for the two substrates. This is explained by the fact that the surface charge on quartz is entirely pH-dependent, while kaolinite has surface faces which carry a permanent negative charge. Adsorption of goethite on to kaolinite increases markedly with increasing NaCl concentration, while adsorption onto quartz is relatively independent of NaCl concentration. This can be explained by the influence of NaCl concentration upon the development of surface charge on the substrates. A method is described for separating surface-bound goethite from free goethite.

Two-step adsorption on jungle-gym-type porous coordination polymers: dependence on hydrogen-bonding capability of adsorbates, ligand-substituent effect, and temperature.

PubMed

Uemura, Kazuhiro; Yamasaki, Yukari; Onishi, Fumiaki; Kita, Hidetoshi; Ebihara, Masahiro

2010-11-01

A preliminary study of isopropanol (IPA) adsorption/desorption isotherms on a jungle-gym-type porous coordination polymer, [Zn(2)(bdc)(2)(dabco)](n) (1, H(2)bdc = 1,4-benzenedicarboxylic acid, dabco =1,4-diazabicyclo[2.2.2]octane), showed unambiguous two-step profiles via a highly shrunk intermediate framework. The results of adsorption measurements on 1, using probing gas molecules of alcohol (MeOH and EtOH) for the size effect and Me(2)CO for the influence of hydrogen bonding, show that alcohol adsorption isotherms are gradual two-step profiles, whereas the Me(2)CO isotherm is a typical type-I isotherm, indicating that a two-step adsorption/desorption is involved with hydrogen bonds. To further clarify these characteristic adsorption/desorption behaviors, selecting nitroterephthalate (bdc-NO(2)), bromoterephthalate (bdc-Br), and 2,5-dichloroterephthalate (bdc-Cl(2)) as substituted dicarboxylate ligands, isomorphous jungle-gym-type porous coordination polymers, {[Zn(2)(bdc-NO(2))(2)(dabco)]·solvents}(n) (2 ⊃ solvents), {[Zn(2)(bdc-Br)(2)(dabco)]·solvents}(n) (3 ⊃ solvents), and {[Zn(2)(bdc-Cl(2))(2)(dabco)]·solvents}(n) (4 ⊃ solvents), were synthesized and characterized by single-crystal X-ray analyses. Thermal gravimetry, X-ray powder diffraction, and N(2) adsorption at 77 K measurements reveal that [Zn(2)(bdc-NO(2))(2)(dabco)](n) (2), [Zn(2)(bdc-Br)(2)(dabco)](n) (3), and [Zn(2)(bdc-Cl(2))(2)(dabco)](n) (4) maintain their frameworks without guest molecules with Brunauer-Emmett-Teller (BET) surface areas of 1568 (2), 1292 (3), and 1216 (4) m(2) g(-1). As found in results of MeOH, EtOH, IPA, and Me(2)CO adsorption/desorption on 2-4, only MeOH adsorption on 2 shows an obvious two-step profile. Considering the substituent effects and adsorbate sizes, the hydrogen bonds, which are triggers for two-step adsorption, are formed between adsorbates and carboxylate groups at the corners in the pores, inducing wide pores to become narrow pores. Interestingly, such

Azobenzene-caged sulforhodamine dyes: a novel class of ‘turn-on’ reactive probes for hypoxic tumor cell imaging

NASA Astrophysics Data System (ADS)

Chevalier, Arnaud; Piao, Wen; Hanaoka, Kenjiro; Nagano, Tetsuo; Renard, Pierre-Yves; Romieu, Anthony

2015-12-01

New sulforhodamine-based fluorescent ‘turn-on’ probes have been developed for the direct imaging of cellular hypoxia. Rapid access to this novel class of water-soluble ‘azobenzene-caged’ fluorophores was made possible through an easily-implementable azo-coupling reaction between a fluorescent primary arylamine derived from a sulforhodamine 101 scaffold (named SR101-NaphtNH 2 ) and a tertiary aniline whose N-substituents are neutral, cationic, or zwitterionic. The detection mechanism is based on the bioreductive cleavage of the azo bond that restores strong far-red fluorescence (emission maximum at 625 nm) by regenerating the original sulforhodamine SR101-NaphtNH 2 . This valuable fluorogenic response was obtained for the three ‘smart’ probes studied in this work, as shown by an in vitro assay using rat liver microsomes placed under aerobic and then under hypoxic conditions. Most importantly, the probe namely SR101-NaphtNH 2 -Hyp-diMe was successfully applied for imaging the hypoxic status of tumor cells (A549 cells).

Facile synthesis of a two-photon fluorescent probe based on pyrimidine 2-isothiocyanate and its application in bioimaging.

PubMed

Yang, Jie; Hu, Wei; Li, Huirong; Hou, Hanna; Tu, Yi; Liu, Bo

2018-04-18

Two-photon microscopy imaging has been widely applied in biological imaging, but the development of two-photon absorption probes is obviously lagging behind in the development of imaging technology. In this paper, a two-photon fluorescent probe (1) based on pyrimidine 2-isothiocyanate has been designed and synthesized through a simple method for two-photon biological imaging. Probe 1 was able to couple effectively with the amino groups on biomolecules. To verify the reactivity of the isothiocyanate group on probe 1 and the amine groups on the biomolecules, d-glucosamine was chosen as a model biomolecule to conjugate with probe 1. The result showed that probe 1 could effectively conjugate with d-glucosamine to synthesize probe 2, and the yield of probe 2 was 83%. After conjugating with d-glucosamine, linear absorption spectra, single-photon fluorescence spectra, and two-photon fluorescence spectra of probes 1 and 2 did not present significant changes. Probes 1 and 2 exhibited high fluorescence quantum yields (0.71-0.79) in toluene and chloroform. They also exhibited different photo-physical properties in solvents with different polarities. The two-photon absorption cross-section of probe 1 was 953 GM in toluene. In addition, probe 1 could be effectively conjugated with transferrin, and the conjugated probe (Tf-1) could be transported into Hep G2 cells through a receptor-mediated process for biological imaging. These results demonstrate that such probes are expected to have great potential applications in two-photon fluorescence bioimaging.

Global Profiling of Reactive Oxygen and Nitrogen Species in Biological Systems

PubMed Central

Zielonka, Jacek; Zielonka, Monika; Sikora, Adam; Adamus, Jan; Joseph, Joy; Hardy, Micael; Ouari, Olivier; Dranka, Brian P.; Kalyanaraman, Balaraman

2012-01-01

Herein we describe a high-throughput fluorescence and HPLC-based methodology for global profiling of reactive oxygen and nitrogen species (ROS/RNS) in biological systems. The combined use of HPLC and fluorescence detection is key to successful implementation and validation of this methodology. Included here are methods to specifically detect and quantitate the products formed from interaction between the ROS/RNS species and the fluorogenic probes, as follows: superoxide using hydroethidine, peroxynitrite using boronate-based probes, nitric oxide-derived nitrosating species with 4,5-diaminofluorescein, and hydrogen peroxide and other oxidants using 10-acetyl-3,7-dihydroxyphenoxazine (Amplex® Red) with and without horseradish peroxidase, respectively. In this study, we demonstrate real-time monitoring of ROS/RNS in activated macrophages using high-throughput fluorescence and HPLC methods. This global profiling approach, simultaneous detection of multiple ROS/RNS products of fluorescent probes, developed in this study will be useful in unraveling the complex role of ROS/RNS in redox regulation, cell signaling, and cellular oxidative processes and in high-throughput screening of anti-inflammatory antioxidants. PMID:22139901

Facet-specific interaction between methanol and TiO2 probed by sum-frequency vibrational spectroscopy.

PubMed

Yang, Deheng; Li, Yadong; Liu, Xinyi; Cao, Yue; Gao, Yi; Shen, Y Ron; Liu, Wei-Tao

2018-04-24

The facet-specific interaction between molecules and crystalline catalysts, such as titanium dioxides (TiO 2 ), has attracted much attention due to possible facet-dependent reactivity. Using surface-sensitive sum-frequency vibrational spectroscopy, we have studied how methanol interacts with different common facets of crystalline TiO 2 , including rutile(110), (001), (100), and anatase(101), under ambient temperature and pressure. We found that methanol adsorbs predominantly in the molecular form on all of the four surfaces, while spontaneous dissociation into methoxy occurs preferentially when these surfaces become defective. Extraction of Fermi resonance coupling between stretch and bending modes of the methyl group in analyzing adsorbed methanol spectra allows determination of the methanol adsorption isotherm. The isotherms obtained for the four surfaces are nearly the same, yielding two adsorbed Gibbs free energies associated with two different adsorption configurations singled out by ab initio calculations. They are ( i ) ∼-20 kJ/mol for methanol with its oxygen attached to a low-coordinated surface titanium, and ( ii ) ∼-5 kJ/mol for methanol hydrogen-bonded to a surface oxygen and a neighboring methanol molecule. Despite similar adsorption energetics, the Fermi resonance coupling strength for adsorbed methanol appears to depend sensitively on the surface facet and coverage.

Determination of adsorption parameters in numerical simulation for polymer flooding

NASA Astrophysics Data System (ADS)

Bao, Pengyu; Li, Aifen; Luo, Shuai; Dang, Xu

2018-02-01

A study on the determination of adsorption parameters for polymer flooding simulation was carried out. The study mainly includes polymer static adsorption and dynamic adsorption. The law of adsorption amount changing with polymer concentration and core permeability was presented, and the one-dimensional numerical model of CMG was established under the support of a large number of experimental data. The adsorption laws of adsorption experiments were applied to the one-dimensional numerical model to compare the influence of two adsorption laws on the historical matching results. The results show that the static adsorption and dynamic adsorption abide by different rules, and differ greatly in adsorption. If the static adsorption results were directly applied to the numerical model, the difficulty of the historical matching will increase. Therefore, dynamic adsorption tests in the porous medium are necessary before the process of parameter adjustment in order to achieve the ideal history matching result.

Structures and Properties of As(OH)3 Adsorption Complexes on Hydrated Mackinawite (FeS) Surfaces: A DFT-D2 Study

PubMed Central

2017-01-01

Reactive mineral–water interfaces exert control on the bioavailability of contaminant arsenic species in natural aqueous systems. However, the ability to accurately predict As surface complexation is limited by the lack of molecular-level understanding of As–water–mineral interactions. In the present study, we report the structures and properties of the adsorption complexes of arsenous acid (As(OH)3) on hydrated mackinawite (FeS) surfaces, obtained from density functional theory (DFT) calculations. The fundamental aspects of the adsorption, including the registries of the adsorption complexes, adsorption energies, and structural parameters are presented. The FeS surfaces are shown to be stabilized by hydration, as is perhaps to be expected because the adsorbed water molecules stabilize the low-coordinated surface atoms. As(OH)3 adsorbs weakly at the water–FeS(001) interface through a network of hydrogen-bonded interactions with water molecules on the surface, with the lowest-energy structure calculated to be an As–up outer-sphere complex. Compared to the water–FeS(001) interface, stronger adsorption was calculated for As(OH)3 on the water–FeS(011) and water–FeS(111) interfaces, characterized by strong hybridization between the S-p and O-p states of As(OH)3 and the surface Fe-d states. The As(OH)3 molecule displayed a variety of chemisorption geometries on the water–FeS(011) and water–FeS(111) interfaces, where the most stable configuration at the water–FeS(011) interface is a bidentate Fe–AsO–Fe complex, but on the water–FeS(111) interface, a monodentate Fe–O–Fe complex was found. Detailed information regarding the adsorption mechanisms has been obtained via projected density of states (PDOS) and electron density difference iso-surface analyses and vibrational frequency assignments of the adsorbed As(OH)3 molecule. PMID:28233994

Retrograde adsorption isotherms: an impossible fact?

PubMed

Helfferich, Friedrich G

2005-06-24

"Retrograde" adsorption isotherms have been reported, but seem to violate thermodynamics and would cause concentration steps to migrate against the direction of fluid-phase flow. In general, what appears to be retrograde behavior is caused by one or more additional, uncontrolled variables. This is illustrated with adsorption of sulfonate on a weak-acid ion exchanger, where adsorption is accompanied by partial conversion of the ion exchanger to the sodium form.

Molecular simulation of methane adsorption characteristics on coal macromolecule

NASA Astrophysics Data System (ADS)

Yang, Zhiyuan; He, Xiaoxiao; Meng, Zhuoyue; Xue, Wenying

2018-02-01

In this paper, the molecular model of anthracite named Wender2 was selected to study the adsorption behaviour of single component CH4 and the competitive adsorption of CH4/CO2, CH4/H2O and CH4/N2. The molecular model of anthracite was established by molecular simulation software (Materials Studio 8.0), and Grand Canonical Monte Carlo (GCMC) simulations were carried out to investigate the single and binary component adsorption. The effects of pressure and temperature on the adsorption position, adsorption energy and adsorption capacity were mainly discussed. The results show that for the single component adsorption, the adsorption capacity of CH4 increases rapidly with the pressure ascending, and then tends to be stable after the first step. The low temperature is favourable for the adsorption of CH4, and the high temperature promotes desorption quantity of CH4 from the coal. Adsorbent molecules are preferentially adsorbed on the edge of coal macromolecules. The order of adsorption capacity of CH4/CO2, CH4/H2O and CH4/N2 in the binary component is H2O>CO2>CH4>N2. The change of pressure has little effect on the adsorption capacity of the adsorbent in the competitive adsorption, but it has a great influence on the adsorption capacity of the adsorbent, and there is a positive correlation between them.

Gold nanoparticles: role of size and surface chemistry on blood protein adsorption

NASA Astrophysics Data System (ADS)

Benetti, F.; Fedel, M.; Minati, L.; Speranza, G.; Migliaresi, C.

2013-06-01

Material interaction with blood proteins is a critical issue, since it could influence the biological processes taking place in the body following implantation/injection. This is particularly important in the case of nanoparticles, where innovative properties, such as size and high surface to volume ratio can lead to a behavioral change with respect to bulk macroscopic materials and could be responsible for a potential risk for human health. The aim of this work was to compare gold nanoparticles (AuNP) and planar surfaces to study the role of surface curvature moving from the macro- to the nano-size in the process of blood protein adsorption. In the course of the study, different protocols were tested to optimize the analysis of protein adsorption on gold nanoparticles. AuNP with different size (10, 60 and 200 nm diameter) and surface coatings (citrate and polyethylene glycol) were carefully characterized. The stabilizing action of blood proteins adsorbed on AuNP was studied measuring the variation of size and solubility of the nanoparticles following incubation with single protein solutions (human serum albumin and fibrinogen) and whole blood plasma. In addition, we developed a method to elute proteins from AuNP to study the propensity of gold materials to adsorb plasma proteins in function of dimensional characteristics and surface chemistry. We showed a different efficacy of the various eluting media tested, proving that even the most aggressive agent cannot provide a complete detachment of the protein corona. Enhanced protein adsorption was evidenced on AuNP if compared to gold laminae (bare and PEGylated) used as macroscopic control, probably due to the superior AuNP surface reactivity.

ADSORPTION MEDIA FOR ARSENIC REMOVAL

EPA Science Inventory

Presentation will discuss the use of adsorptive media for the removal of arsenic from drinking water. Presentation is a fundamental discussion on the use of adsorptive media for arsenic removal and includes information from several EPA field studies on removal of arsenic from dr...

Adsorption And Simultaneous Dechlorination Of PCBs On GAC/Fe/Pd: Mechanistic Aspects And Reactive Capping Barrier Concept

EPA Science Inventory

There are many concerns and challenges in current remediation strategies for sediments contaminated with polychlorinated biphenyls (PCBs). Our efforts have been geared toward the development of granular activated carbon (GAC) impregnated with reactive iron/palladium (Fe/Pd) bime...

Application of porous metal enrichment probe sampling to single cell analysis using matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS).

PubMed

Fu, Qiang; Tang, Jun; Cui, Meng; Xing, Junpeng; Liu, Zhiqiang; Liu, Shuying

2016-01-01

There is an increasing need for analyzing metabolism in a single cell, which is important to understand the nature of cellular heterogeneity, disease, growth and specialization, etc. However, single cell analysis is often challenging for the traces of samples. In the present study, porous metal enrichment probe sampling combined with matrix-assisted laser desorption ionization time of flight mass spectrometry (MALDI-TOF-MS) has been applied for in situ analysis of live onion epidemic cell. Porous probe, treated by corroding copper wire with HCl, was directly inserted into a single cell to get cell solution. A self-made linear actuator was enough to control the penetration of probe into the target cell accurately. Then samples on the tip of probe were eluted and detected by a commercial MALDI-TOF-MS directly. The formation of porous microstructure on the probe surface increased the adsorptive capacity of cell solution. The sensitivity of porous probe sampling was 6 times higher than uncorroded probes generally. This method provides a sensitive and convenient way for the sampling and detection of single cell solution. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

Mechanics of adsorption-deformation coupling in porous media

NASA Astrophysics Data System (ADS)

Zhang, Yida

2018-05-01

This work extends Coussy's macroscale theory for porous materials interacting with adsorptive fluid mixtures. The solid-fluid interface is treated as an independent phase that obeys its own mass, momentum and energy balance laws. As a result, a surface strain energy term appears in the free energy balance equation of the solid phase, which further introduces the so-called adsorption stress in the constitutive equations of the porous skeleton. This establishes a fundamental link between the adsorption characteristics of the solid-fluid interface and the mechanical response of the porous media. The thermodynamic framework is quite general in that it recovers the coupled conduction laws, Gibbs isotherm and the Shuttleworth's equation for surface stress, and imposes no constraints on the magnitude of deformation and the functional form of the adsorption isotherms. A rich variety of coupling between adsorption and deformation is recovered as a result of combining different poroelastic models (isotropic vs. anisotropic, linear vs. nonlinear) and adsorption models (unary vs. mixture adsorption, uncoupled vs. stretch-dependent adsorption). These predictions are discussed against the backdrop of recent experimental data on coal swelling subjected to CO2 and CO2sbnd CH4 injections, showing the capability and versatility of the theory in capturing adsorption-induced deformation of porous materials.

Physicochemical factors affecting ethanol adsorption by activated carbon.

PubMed

Bradley, K J; Hamdy, M K; Toledo, R T

1987-03-01

Powder and granular activated charcoal were evaluated for ethanol adsorptivity from aqueous mixtures using an adsorption isotherm. Ethanol adsorption capacity was more pronounced at 25 degrees C as compared to 5, 15, and 40 degrees C. When pH of the ethanol-buffer mixture (0.09 ionic strength) was changed from acidic (2.3) to neutral and then to alkaline (11.2), ethanol adsorption was decreased. Increasing ionic strength of the ethanol-buffer mixtures from 0.05 to 0.09 enhanced ethanol adsorption but a further increase to 0.14 showed no significant effect. Ethanol adsorption was more efficient from an aqueous ethanol mixture as compared to semidefined and nondefined fermentation worts, respectively. Heating granular charcoal to 400 degrees C for 1 h and 600 degrees C for 3 h in N(2) increased ethanol adsorptivity and heating to 1000 degrees C (1 h) in CO(2) decreased it when ethanol was removed from dilute solutions by simple pass adsorption in a carbon packed column. Granular charcoal was superior to powdered charcoal and an inverse relationship was noted between the weight of the granular carbon bed in the column and ethanol adsorbed/g carbon. Decreasing the column feed flow rate from 7.5 to 2.0 L aqueous ethanol/min increased the adsorption rate.

Investigation of the micropolarity of reverse micelles using quinolinium betaine compounds as probes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ueda, Mitsuo; Kimura, Akimune; Wakida, Tomoji

1994-03-15

There is considerable interest in the utilization of reverse micelle and microemulsion systems in a variety of applications such as reactivity control, tertiary oil recovery, solar energy conversion, enzyme mediated synthesis, etc. Fundamental to understanding improved applications of such systems are questions concerning solubilization; thus substantial efforts have been focused on the investigation of the solubilizing state of the assemblies. N-octyl-quinolinium betaine is introduced as an absorption probe for the micropolarity of the interior of reverse micelles. its solubilization by reverse micelles and water/oil microemulsions of Aerosol-OT in isooctane is compared with that of N-methyl-quinolinium betaine at various water contentsmore » of the solution. Analysis of the excitation energies in the visible range of the spectrum indicates that the methyl derivative probes the polarity of the aqueous pool of the micelle, whereas the octyl derivative behaves as a cosurfactant probe that reports on the polarity of the water/oil interfacial region.« less