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1.
Calculations of the size and density of atmospheric aerosols are complicated by the fact that they can exist at concentrations highly supersaturated with respect to dissolved salts and supercooled with respect to ice. Densities and apparent molar volumes of solutes in aqueous solutions containing the solutes H(2)SO(4), HNO(3), HCl, Na(2)SO(4), NaNO(3), NaCl, (NH(4))(2)SO(4), NH(4)NO(3), and NH(4)Cl have been critically evaluated and represented using fitted equations from 0 to 50 °C or greater and from infinite dilution to concentrations saturated or supersaturated with respect to the dissolved salts. Using extrapolated densities of high-temperature solutions and melts, the relationship between density and concentration is extended to the hypothetical pure liquid solutes. Above a given reference concentration of a few mol kg(-1), it is observed that density increases almost linearly with decreasing temperature, and comparisons with available data below 0 °C suggest that the fitted equations for density can be extrapolated to very low temperatures. As concentration is decreased below the reference concentration, the variation of density with temperature tends to that of water (which decreases as temperature is reduced below 3.98 °C). In this region below the reference concentration, and below 0 °C, densities are calculated using extrapolated apparent molar volumes which are constrained to agree at the reference concentrations with an equation for the directly fitted density. Calculated volume properties agree well with available data at low temperatures, for both concentrated and dilute solutions. Comparisons are made with literature data for temperatures of maximum density. Apparent molar volumes at infinite dilution are consistent, on a single ion basis, to better than ±0.1 cm(3) mol(-1) from 0 to 50 °C. Volume properties of aqueous NaHSO(4), NaOH, and NH(3) have also been evaluated, at 25 °C only. In part 2 of this work (ref 1 ) an ion interaction (Pitzer) model has been used to calculate apparent molar volumes of H(2)SO(4) in 0-3 mol kg(-1) aqueous solutions of the pure acid and to represent directly the effect of the HSO(4)(-) ? H(+) + SO(4)(2-) reaction. The results are incorporated into the treatment of aqueous H(2)SO(4) density described here. Densities and apparent molar volumes from -20 to 50 °C, and from 0 to 100 wt % of solute, are tabulated for the electrolytes listed in the title and have also been incorporated into the extended aerosol inorganics model (E-AIM, http://www.aim.env.uea.ac.uk/aim/aim.php) together with densities of the solid salts and hydrates.  相似文献   

2.
The stable form of adsorbed sulfur species and their coverage were investigated on Rh, Ni, and Rh-Ni binary metal surfaces using density functional theory calculations and the ab initio thermodynamics framework. S adsorption, SO(x) (x = 1-4) adsorption, and metal sulfide formation were examined on Rh(111) and Ni(111) pure metals. Both Rh and Ni metals showed a preference for S surface adsorption rather than SO(x) adsorption under steam reforming conditions. The transition temperature from a clean surface (<(1)/(9) ML) to S adsorption was identified on Rh(111), Ni(111), Rh(1)Ni(2)(111), and Rh(2)Ni(1)(111) metals at various P(H(2))/P(H(2)S) ratios. Bimetallic Rh-Ni metals transition to a clean surface at lower temperatures than does the pure Rh metal. Whereas Rh is covered with (1)/(3) ML of sulfur under the reforming conditions of 4-100 ppm S and 800 °C, Rh(1)Ni(2) is covered with (1)/(9) ML of sulfur at the lower end of this range (4-33 ppm S). The possibility of sulfate formation on Rh catalysts was examined by considering higher oxygen pressures, a Rh(221) stepped surface, and the interface between a Rh(4) cluster and CeO(2)(111) surface. SO(x) surface species are stable only at high oxygen pressure or low temperatures outside those relevant to the steam reforming of hydrocarbons.  相似文献   

3.
Aqueous surfaces act as a gateway to absorption and aqueous-phase reaction of gases in the atmosphere. The composition of aerosols varies greatly and is expected to influence the structure of the interface. For example, aldehydes comprise a significant fraction of atmospheric organics and are likely to accumulate at aqueous surfaces. But it is difficult to anticipate their effect on the migration of gaseous species through the interfacial region. Surface organics may act as a barrier to absorption, or they may facilitate uptake via cooperative interactions with absorbing compounds. The surface spectroscopic studies presented here examine the nature of the vapor/water interface during uptake of SO(2) to aqueous formaldehyde solutions, elucidating the role of surface species in a multicomponent interfacial system. The results show that the product of the reaction between SO(2) and formaldehyde, hydroxymethanesulfonate, shows a surface affinity that is enhanced in the presence of SO(2).  相似文献   

4.
Adsorption of SO(2) in the presence of O(2) on Pt/C catalysts often used as electrocatalysts has been investigated by temperature programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). The amounts of SO(2) adsorption on Pt/C in the presence of O(2) were much higher than those in the absence of O(2) (SO(2)-N(2)) and from the carbon support (Vulcan XC-72) alone. Adsorption is dependent on oxygen concentration over the range 0-20% but reaches saturation at 20% O(2). The spillover of SO(2) from Pt to the carbon support has been proposed for 10, 20, and 40% Pt loadings, characterized by desorption temperatures of approximately 150 and 260 °C for SO(2) adsorbed on Pt and carbon, respectively. Adsorbed Pt-S, C-S, C-SO(x), and Pt-SO(4) species were identified by XPS as S-containing species on both Pt and carbon. Both TPD and XPS indicate that the carbon support plays a major role in SO(2) adsorption, primarily as SO(x) (x = 3, 4). The bonding of S and SO(x) on the carbon support was strong enough that back diffusion to the Pt surface did not occur.  相似文献   

5.
The rate of cyclohexane photo-catalytic oxidation to cyclohexanone over anatase TiO(2) was studied at temperatures between 23 and 60 °C by in situ ATR-FTIR spectroscopy, and the kinetic parameters were estimated using a microkinetic model. At low temperatures, surface cyclohexanone formation is limited by cyclohexane adsorption due to unfavorable desorption of H(2)O, rather than previously proposed slow desorption of the product cyclohexanone. Up to 50 °C, the activation energy for photocatalytic cyclohexanone formation is zero, while carboxylates are formed with an activation energy of 18.4 ± 3.3 kJ mol(-1). Above 50 °C, significant (thermal) oxidation of cyclohexanone contributes to carboxylate formation. The irreversibly adsorbed carboxylates lead to deactivation of the catalyst, and are most likely the predominant cause of the non-Arrhenius behavior at relatively high reaction temperatures, rather than cyclohexane adsorption limitations. The results imply that elevating the reaction temperature of photocatalytic cyclohexane oxidation reduces selectivity, and is not a means to suppress catalyst deactivation.  相似文献   

6.
Thermoresponsive gelling behavior of concentrated alumina suspensions with poly(acrylic acid) (PAA) and triblock copolymer (PEO(101)-PPO(56)-PEO(101), Pluronic F127) was investigated as a function of PAA concentration (0.4-1.2 mass%) for ceramic solid free forming. The copolymer species assemble into micelles at temperatures above 15°C, yielding aqueous physical gel. In this study, the concentrated alumina aqueous suspensions (φ=35 vol%) were first prepared using the anionic dispersant of PAA, and then the copolymer species (10 mass%) were dissolved at a cooled temperature at 10°C. The addition of the copolymer species had a negligible influence on the adsorption state of PAA onto the alumina surfaces. The PAA concentration needed for the saturation adsorption on the alumina surfaces was ~0.6 mass%. When the PAA concentration was this value or slightly less, the suspension became gel state at 30°C from low viscous state at 10°C. The thermally induced alumina gel had excellent viscoelastic properties, and thereby the three dimensional periodic ceramic structures were successfully fabricated by a direct colloidal printing method that using the gels as "solid" inks at the room temperature. On the other hand, when it exceeded the saturation adsorption limit, the gelling behavior was not observed, indicating that the non-adsorbing PAA species may partly suppress the micellization of the copolymer on the heating.  相似文献   

7.
The thermodynamics of adsorption of gallic acid (GA, 3,4,5-trihydroxylbenzoic acid) on the hanging mercury drop electrode (HMDE) surface was studied by temperature-dependent stripping voltammetry (TD-SV), at physiological pH 7.4. The thermodynamic parameters, e.g., Gibbs free energy, ΔG(ADS), enthalpy, ΔΗ(ADS) and entropy, ΔS(ADS), of adsorption have been determined at physiological temperatures 2-40 °C. Chemisorption of the radical species ≡[GA(OH)(2)(O(-))]* is the energetically important reaction. The thermodynamic data show a complex mechanism of adsorption of GA on the electrode surface, which is strongly dependent on temperature. At low-temperatures T<12 °C, adsorption is controlled by enthalpy, while at T>22 °C, adsorption is entropy driven. In the temperature range 12 °C and 22 °C, a combined enthalpy-entropy stabilization occurs. A mechanism is proposed which analyses the implication of thermodynamics to the interfacial adsorption of polyphenols with cell membranes under physiological conditions.  相似文献   

8.
The determination of enthalpies of reactions (aqueous and surface complexation) is used in this work to model the temperature effect on the adsorption processes. Microcalorimetry experiments were carried out to determine the enthalpy of adsorption of europium on γ-alumina at 25 °C. The stability constants at 50 °C were then calculated with the van't Hoff equation, and a 2-pK approach was used to model the adsorptive behavior of Eu on alumina at 50 °C, as a function of pH. The results have shown that the adsorption of Eu(3+) on the alumina surface is weakly endothermic. In the experimental conditions considered in the present study, the temperature has only a small effect on the adsorption reaction.  相似文献   

9.
The orientation and hydrogen bonding of water molecules in the vapor/water interfacial region in the presence of SO2 and CO2 gas are examined using vibrational sum-frequency spectroscopy (VSFS) to gain insight into the adsorption and reactions of these gases in atmospheric aerosols. The results show that an SO2 surface complex forms when the water surface is exposed to an atmosphere of SO2 gas. Reaction of SO2 with interfacial water leads to other spectral changes that are examined by studying the VSF spectra and surface tension isotherms of several salts added to the aqueous phase, specifically NaHSO3, NaHCO3, Na2SO3, Na2CO3, Na2SO4, and NaHSO4. The results are compared with similar studies of CO2 adsorption and reaction at the surface. A weakly bound surface complex is not observed with CO2.  相似文献   

10.
The adsorption of sodium bis 2-ethylhexyl sulfosuccinate, NaAOT, to a sapphire surface from aqueous solution has been studied by neutron reflection at concentrations above the critical micelle concentration (cmc). Complementary measurements of the bulk structure were made with small-angle neutron scattering and grazing incidence small-angle neutron scattering. At a concentration of about 1% wt (10 × cmc), lamellar phase NaAOT was observed both at the surface and in the bulk. The structure seen at the interface for a solution of 2% wt NaAOT is a 35 ± 2 ? thick bilayer adsorbed to the sapphire surface at maximum packing density, followed by an aligned stack of fluctuating bilayers of thickness 51 ± 2 ? and with an area per molecule of 40 ± 2 ?(2). Each bilayer is separated by a water: at 25 °C, this layer is 148 ± 2 ?. A simple model for the reflectivity from fluctuating layers is presented, and for 2.0% wt NaAOT the fluctuations were found to have an amplitude of 25 ± 5 ?. The temperature sensitivity of the structure at the surface was investigated in the range 15-30 °C. The effect of temperature was pronounced, with the solvent layer becoming thinner and the volume occupied by the NaAOT molecules in a bilayer increasing with temperature. The amplitude of the fluctuations, however, is approximately temperature independent in this range. The adsorption of NaAOT at the sapphire surface resembles that previously found at hydrophilic and hydrophobic silica surfaces. The coexisting bulk lamellar phase has a spacing of layers similar to that observed at the surface. These observations are an indication that the major driving force for adsorption is self-assembly, independent of the chemical nature of the interface.  相似文献   

11.
The micellization of the ionic liquid N-alkyl-N-methylpyrrolidinium bromide (C(n)MPB, n = 12, 14 and 16) in aqueous solutions was investigated by surface tension measurements, electrical conductivity and static luminescence quenching. The effectiveness of the surface tension reduction (Π(cmc)), maximum surface excess concentration (Γ(max)) and the minimum area (A(min)) occupied per surfactant molecule at the air/water interface can be obtained from the surface tension measurements at 25 °C. The critical micelle concentration (cmc) at different temperatures and a series of thermodynamic parameters (ΔG, ΔH and ΔS) of micellization were evaluated from electrical conductivity measurements in the temperature range of 25-45 °C. The thermodynamic parameters show that the micelle formation is entropy-driven at low temperature and enthalpy-driven at high temperature. Furthermore, the micelle aggregation number (N(agg)) of C(n)MPB was calculated according to the Turro-Yekta method through static luminescence quenching and found that N(agg) (49, 55, and 59) increased with the hydrophobic chain length of C(n)MPB.  相似文献   

12.
Interactions between porous silicon (pSi) particles and probe molecules were evaluated to determine the effect of pSi and probe molecule chemistry on adsorption. Methylene blue, ethyl violet and orange G dyes were chosen for investigation as they possess distinct functionalities and charges. Several distinct pSi surface species were produced via thermal oxidation at 200-800 °C and their effect on adsorption investigated. The adsorption mechanisms were elucidated from equilibrium adsorption and desorption isotherms. Methylene blue adsorption was attributed to electrostatic attraction where a gradual increase in adsorption with oxidation temperature was observed. Significant methylene blue desorption was observed at pH 3, confirming adsorption occurs via electrostatic attraction. Ethyl violet demonstrated an increase in plateau adsorption capacity and affinity with increased oxidation temperatures and adsorption was initially attributed to electrostatic attraction, however desorption of ethyl violet was not observed, thus indicating potential chemisorption. Orange G exhibited high affinity adsorption for Si(y)SiH(x) terminated surfaces but no orange G desorption was detected, indicating a chemisorption adsorption mechanism. It has been successfully demonstrated that the surface modification of pSi enabled the manipulation of molecular interactions. By interacting probe molecules with similar functionalities to drug molecule with pSi, greater understanding of drug-pSi interactions can be ascertained which are of great importance. pSi surface chemistry can be tailored to enable control over molecular interactions and ultimately dictate loading, encapsulation and release behavior.  相似文献   

13.
张兰辉  朱步瑶  赵国玺 《化学学报》1992,50(11):1041-1045
研究了四种氧杂氟表面活性及其与同电性直链碳氢表面活性剂混合体系的表面活性;考察了混合体系中的表面吸附和胶团形成现象.在吸附层中分子间有明显的互疏作用,在溶液中倾向于各自形成胶团.还讨论了反离子结合度不同对理想混合胶团的组成CMC的计算的影响,提出了一般的计算式,实验测得这些氧杂氟表面活性剂有较低的胶团反离子结合度.  相似文献   

14.
Melamine formaldehyde resins were synthesized with encapsulated CaCl(2) as a template. Carbonization at high temperatures led to the formation of carbon materials containing N atoms. Washing with de-ionized water removed encapsulated CaCl(2), resulting in the formation of mesopores (3-30 nm) with the high surface areas (770-1300 m(2)/g). The template can be recycled and the method is simple and cost effective as compared to the hard template techniques. The mesoporous carbons containing nitrogen (NMC) thus prepared exhibited the amphipathic surfaces (both hydrophilic and lipophilic) and adsorbed great amount of water and benzene. In addition, the incorporated N atoms exhibited quite strong basicity for the adsorption of great amount of SO(2).  相似文献   

15.
Porous anodic alumina (PAA) is a well-defined material that has found many applications. The range of applications toward sensing and recognition can be greatly expanded if the alumina surface is covalently modified with an organic monolayer. Here, we present a new method for the organic modification of PAA based on the reaction of terminal alkynes with the alumina surface. The reaction results in the the formation of a monolayer within several hours at 80 °C and is dependent on both oxygen and light. Characterization with X-ray photoelectron spectroscopy and infrared spectroscopy indicates formation of a well-defined monolayer in which the adsorbed species is an oxidation product of the 1-alkyne, namely, its α-hydroxy carboxylate. The obtained monolayers are fairly stable in water and at elevated temperatures, as was shown by monitoring the water contact angle. Modification with 1,15-hexadecadiyne resulted in a surface that has alkyne end groups available for further reaction, as was demonstrated by the subsequent reaction of N-(11-azido-3,6,9-trioxaundecyl)trifluoroacetamide with the modified surface. Biofunctionalization was explored by coupling 11-azidoundecyl lactoside to the surface and studying the subsequent adsorption of the lectin peanut agglutinin (PNA) and the yeast Candida albicans, respectively. Selective and reversible binding of PNA to the lactosylated surfaces was demonstrated. Moreover, PNA adsorption was higher on surfaces that exposed the β-lactoside than on those that displayed the α anomer, which was attributed to surface-associated steric hindrance. Likewise, the lactosylated surfaces showed increased colonization of C. albicans compared to unmodified surfaces, presumably due to interactions involving the cell wall β-glucan. Thus, this study provides a new modification method for PAA surfaces and shows that it can be used to induce selective adsorption of proteins and microorganisms.  相似文献   

16.
Precipitation polymerization of N-isopropylacrylamide (NIPAM) with methylenebisacrylamide (MBAAm) in water at 70°C gave thermosensitive hydrogel microspheres. The adsorbability of proteins on the poly-NIPAM microspheres was found to depend on temperature. Below the lower critical solution temperature (LCST) of poly-NIPAM in an aqueous medium, that is, around 32°C, the microspheres hold a large amount of water inside and their surface is hydrophilic enough to suppress the adsorption of proteins. On the contrary, above 32°C, the micropheres deswell and their surface becomes hydrophobic and, consequently, susceptible to adsorption of a large amount of proteins. Proteins once adsorbed on the microspheres at a high temperature could be desorbed more or less by lowering the temperature to below 32°C. The extent of desorption at low temperatures was found to depend on the incubation time for adsorption at high temperatures.  相似文献   

17.
Strategies to modify metal oxide surfaces are important because of the increasing applications of metal oxides in catalysis, sensing, electronics, and renewable energy. Here, we report the formation of molecular monolayers on anatase nanocrystalline TiO(2) surfaces at near-ambient temperatures by a simple one-step immersion. This is achieved by an analogue of the Williamson ether synthesis, in which the hydroxyl groups of the TiO(2) surface react with iodo-alkane molecules to release HI and form a Ti-O-C surface linkage. The grafted molecules were characterized by Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) to confirm the formation of covalently bonded monolayers. Kinetic studies yielded an activation barrier of ~59 kJ/mol for the grafting reaction. Measurements of hydrolytic stability of the grafted molecules in water show that approximately half the molecules are removed within minutes to hours at temperatures of 25-100 °C with an activation energy of ~82 kJ/mol, while the remaining molecules are stable for much longer periods of time. These different stabilities are discussed in terms of the different types of Ti-O-C bonds that can form on TiO(2) surfaces.  相似文献   

18.
In-depth probing of the surface electronic structure on solid oxide fuel cell (SOFC) cathodes, considering the effects of high temperature, oxygen pressure, and material strain state, is essential toward advancing our understanding of the oxygen reduction activity on them. Here, we report the surface structure, chemical state, and electronic structure of a model transition metal perovskite oxide system, strained La(0.8)Sr(0.2)CoO(3) (LSC) thin films, as a function of temperature up to 450 °C in oxygen partial pressure of 10(-3) mbar. Both the tensile and the compressively strained LSC film surfaces transition from a semiconducting state with an energy gap of 0.8-1.5 eV at room temperature to a metallic-like state with no energy gap at 200-300 °C, as identified by in situ scanning tunneling spectroscopy. The tensile strained LSC surface exhibits a more enhanced electronic density of states (DOS) near the Fermi level following this transition, indicating a more highly active surface for electron transfer in oxygen reduction. The transition to the metallic-like state and the relatively more enhanced DOS on the tensile strained LSC at elevated temperatures result from the formation of oxygen vacancy defects, as supported by both our X-ray photoelectron spectroscopy measurements and density functional theory calculations. The reversibility of the semiconducting-to-metallic transitions of the electronic structure discovered here, coupled to the strain state and temperature, underscores the necessity of in situ investigations on SOFC cathode material surfaces.  相似文献   

19.
Adsorption of sulfur dioxide on hematite and goethite particle surfaces   总被引:1,自引:0,他引:1  
The adsorption of sulfur dioxide (SO(2)) on iron oxide particle surfaces at 296 K has been investigated using X-ray photoelectron spectroscopy (XPS). A custom-designed XPS ultra-high vacuum chamber was coupled to an environmental reaction chamber so that the effects of adsorbed water and molecular oxygen on the reaction of SO(2) with iron oxide surfaces could be followed at atmospherically relevant pressures. In the absence of H(2)O and O(2), exposure of hematite (alpha-Fe(2)O(3)) and goethite (alpha-FeOOH) to SO(2) resulted predominantly in the formation of adsorbed sulfite (SO(3)(2-)), although evidence for adsorbed sulfate (SO(4)(2-)) was also found. At saturation, the coverage of adsorbed sulfur species was the same on both alpha-Fe(2)O(3) and alpha-FeOOH as determined from the S2p : Fe2p ratio. Equivalent saturation coverages and product ratios of sulfite to sulfate were observed on these oxide surfaces in the presence of water vapor at pressures between 6 and 18 Torr, corresponding to 28 to 85% relative humidity (RH), suggesting that water had no effect on the adsorption of SO(2). In contrast, molecular oxygen substantially influenced the interactions of SO(2) with iron oxide surfaces, albeit to a much larger extent on alpha-Fe(2)O(3) relative to alpha-FeOOH. For alpha-Fe(2)O(3), adsorption of SO(2) in the presence of molecular oxygen resulted in the quantitative formation of SO(4)(2-) with no detectable SO(3)(2-). Furthermore, molecular oxygen significantly enhanced the extent of SO(2) uptake on alpha-Fe(2)O(3), as indicated by the greater than two-fold increase in the S2p : Fe2p ratio. Although SO(2) uptake is still enhanced on alpha-Fe(2)O(3) in the presence of molecular oxygen and water, the enhancement factor decreases with increasing RH. In the case of alpha-FeOOH, there is an increase in the amount of SO(4)(2-) in the presence of molecular oxygen, however, the predominant surface species remained SO(3)(2-) and there is no enhancement in SO(2) uptake as measured by the S2p : Fe2p ratio. A mechanism involving molecular oxygen activation on oxygen vacancy sites is proposed as a possible explanation for the non-photochemical oxidation of sulfur dioxide on iron oxide surfaces. The concentration of these sites depends on the exact environmental conditions of RH.  相似文献   

20.
We study the adsorption of a symmetric triblock copolymer of ethylene oxide, EO, and propylene oxide, PO, end-capped with quarternized poly(2-dimethylaminoethyl methacrylate), DMAEMA (DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24)). Light scattering and tensiometry are used to measure the relative size of the associated structures and surface excess at the air-liquid interface. The adsorbed amount, the amount of coupled water, and the viscoelasticity of the adsorbed polymer layer are measured on hydrophobic and hydrophilic surfaces (polypropylene, cellulose, and silica) by using quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR) at different ionic strengths and temperatures. The results of the experiments are compared with those obtained after adsorption of the uncharged precursor copolymer, without the cationic end-caps (EO(132)PO(50)EO(132)). DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) possesses higher affinity with the negatively charged silica and cellulose surfaces while the uncharged copolymer adsorbs to a larger extent on polypropylene surfaces. In this latter case, adsorption increases with increasing solution ionic strength and temperature. Adsorption of EO(132)PO(50)EO(132) on silica surfaces has little effect on the water contact angle (WCA), while adsorption of DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) increases the WCA of silica to 32°, indicating a large density of exposed PPO blocks upon adsorption. After adsorption of EO(132)PO(50)EO(132) and DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) on PP, the WCA is reduced by ≈14° and ≈28°, respectively, due to the exposed hydrophilic EO and highly water-soluble DMAEMA segments on the surfaces. The extent of surface coverage at saturation at the polypropylene/liquid interfaces (≈31 and 40 nm(2)/molecule obtained by QCM and SPR, respectively) is much lower, as expected, when compared with results obtained at the air/liquid interface, where a tighter packing is observed. The percentage of water coupled to the adsorbed cationic polymer decreases with solution ionic strength. Overall, these observations are ascribed to the effects of electrostatic screening, polymer hydrodynamic size, and solvency.  相似文献   

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