Vibrational spectroscopy characterization of impregnated activated carbon adsorption of H2S.

Activated carbon filters are used for the removal of hazardous gases from the air. This research applied vibrational spectroscopy methods, including Fourier-transform infrared spectroscopy and Raman spectroscopy to characterize hydrogen sulfide adsorption on impregnated carbon materials with metals having reactivity toward hydrogen sulfide. The Fourier-transform infrared spectroscopy results demonstrated the formation of a new chemical bond between the impregnating metals and the sulfur, indicated by the appearance of a new band at 618 cm-1. The Raman spectra results showed that for the copper-impregnated activated carbon with the highest hydrogen sulfide adsorption capacity, a new vibrational band at 475 cm-1 evolved, indicating a copper-sulfur bond. In addition, upshifts in the carbon D sub-bands were observed after efficient hydrogen sulfide adsorption, along with a larger area of the approximately 1500 cm-1 band. Therefore, Fourier-transform infrared spectroscopy and Raman spectroscopy combination can potentially indicate H2S adsorption on impregnated activated carbon filters.

Phosphate Additives for Aging Inhibition of Impregnated Activated Carbon against Hazardous Gases.

Impregnated activated carbons (IACs) used in air filtration gradually lose their efficacy for the chemisorption of noxious gases when exposed to humidity due to impregnated metal deactivation. In order to stabilize IACs against aging, and to prolong the filters' shelf life, inorganic phosphate compounds (phosphoric acid and its three salts, NaHPO4, Na2HPO4, and Na3PO4) were used as anti-aging additives for two different chromium-free IACs impregnated with copper, zinc, molybdenum, and triethylenediamine (TEDA). Phosphoric acid, monosodium, and disodium phosphate were found to be very efficient in inhibiting the aging of IACs over long periods against cyanogen chloride (the test agent) chemisorption, with the latter being the most efficient. However, the efficiency of phosphate as an anti-aging additive was not well correlated with its ability to inhibit the migration of metal impregnants, especially copper, from the interior to the external surface of carbon granules. Unlike organic additives, the inorganic phosphate additives did not decrease the surface area of the IAC or its physical adsorption capacity for toluene. Using a phosphate additive in IAC used in collective protection and personal filters can improve the safety of the user and the environment and dramatically reduce the need to replace these filters after exposure to humid environments. This has safety, economic, logistical, and environmental advantages.

The effects of aging on the dynamic adsorption of hazardous organic vapors on impregnated activated carbon.

The effects of an eight-year natural aging of ASC impregnated activated carbon on the adsorption capacity and breakthrough times of model organic vapors and of the nerve agent sarin were investigated. Aging delayed methanol breakthrough from dry air on pre-dried carbon, but shortened the breakthrough time of both methanol and hexane under relative humidity (RH) of 30-85% on pre-humidified carbon. Aging also shortened the breakthrough time of the less volatile model compound 2-methoxyethanol, especially under RH of 60-85%. Aging significantly reduced the protection capacity against sarin at RH of 85%. The effects of aging on physisorption are attributed to enhanced hydrogen-bonding capability and strength of the interaction between water and adsorption sites on the carbon surface.

Imaging and Chemical Analysis of External and Internal Ureteral Stent Encrustation.

Introduction: Ureteral stents are effective in alleviating flow disruptions in the urinary tract, whether due to ureteral stones, strictures or extrinsic ureteral obstruction. However, significant stent encrustation on the external and/or internal stent lumen walls can occur, which may interfere with stent functioning and/or removal. Currently, there is only limited, generally qualitative, information on the distribution, mineral structure, and chemical content of these deposits, particularly in terms of stent lumen encrustation. Objective: To quantify, in an initial investigation, external and internal encrustation in representative, intact ureteral stents. The study investigates possible correlations between patterns of external and internal encrustation, determines mineral structure and chemical composition, and examines the potential for stent lumen obstruction even in the absence of external stent wall encrustation. Study Design: High-resolution, laboratory micro-computed tomography (micro-CT) was used to non-destructively image external and internal stent encrustation in four representative stents. X-ray diffractometry (XRD) and scanning electron microscopy-energy dispersive x-ray spectroscopy (SEM-EDS) enabled parallel analysis of mineral structure and chemical content of samples collected from external and internal encrusted material along the distal, proximal and mid-ureteral stent regions. Results: Extensive stent lumen encrustation can occur within any region of a stent, with only incidental or minor external encrustation, along the entire length of the stent. External and internal encrusted materials in a given stent are generally similar, consisting of a combination of amorphous (mostly organic) and crystalline mineral deposits. Conclusion: Micro-CT demonstrates that significant stent lumen encrustation can occur, which can lead to partial or full stent lumen occlusion, even when the exterior stent wall is essentially free of encrusted material.

Influence of Single Stent Size and Tandem Stents Subject to Extrinsic Ureteral Obstruction and Stent Occlusion on Stent Failure.

Background and Purpose: Drainage of obstructed kidney attributable to extrinsic ureteral obstruction (EUO), required to prevent renal damage, is often achieved using Double-J ureteral stents. However, these stents fail frequently, and there is considerable debate regarding what stent size, type, and configuration offer the best option for sustained drainage. In this study, we examine the impact of stent diameter and choice of single/tandem configuration, subject to EUO and various degrees of stent occlusion, on stent failure. Materials and Methods: Computational fluid dynamics simulations and an in vitro ureter-stent experiment enabled quantification of flow behavior in stented ureters subject to EUO and stent occlusions. Various single and tandem stents under EUO were considered. In each simulation and experiment, changes in renal pressure were monitored for different degrees of stent lumen occlusion, and onset of stent failure as well as simulated distributions of fluid flow between stent and ureter lumina were determined. Results: For an encircling EUO that completely obstructs the ureter lumen, with or without partial stent occlusion, the choice of stent size/configuration has little effect on renal pressure. The pressure increases significantly for ∼90% stent lumen occlusion, with failure at >95% occlusion, independent of stent diameter or a tandem configuration, and with little influence of occlusion length along the stent. Conclusions: Stent failure rate is independent of stent diameter or single/tandem configuration, for the same percentage of stent lumen occlusion, in this model. Stent failure incidence may decrease for larger diameter stents and tandem configurations, because of the larger luminal area.

Studying the Physical and Chemical Properties of Polydimethylsiloxane Matrix Reinforced by Nanostructured TiO2 Supported on Mesoporous Silica.

In this study, a reactive adsorbent filler was integrated into a polymeric matrix as a novel reactive protective barrier without undermining its mechanical, thermal, and chemical properties. For this purpose, newly synthesized TiO2/MCM/polydimethylsiloxane (PDMS) composites were prepared, and their various properties were thoroughly studied. The filler, TiO2/MCM, is based on a (45 wt%) TiO2 nanoparticle catalyst inside the pores of ordered mesoporous silica, MCM-41, which combines a high adsorption capacity and catalytic capability. This study shows that the incorporation of TiO2/MCM significantly enhances the composite's Young's modulus in terms of tensile strength, as an optimal measurement of 1.6 MPa was obtained, compared with that of 0.8 MPa of pristine PDMS. The composites also showed a higher thermal stability, a reduction in the coefficient of thermal expansion (from 290 to 110 ppm/°C), a 25% reduction in the change in the normalized specific heat capacity, and an increase in the thermal degradation temperatures. The chemical stability in organic environments was improved, as toluene swelling decreased by 40% and the contact angle increased by ~15°. The enhanced properties of the novel synthesized TiO2/MCM/PDMS composite can be used in various applications where a high adsorption capacity and catalytic/photocatalytic activity are required, such as in protective equipment, microfluidic applications, and chemical sensor devices.

Failure of ureteral stents subject to extrinsic ureteral obstruction and stent occlusions.

PURPOSE: To quantify the occurrence of stent failure and the dynamic behavior of urine flow in ureter-stent systems, including the relative flow in the ureter and stent lumina, subject to various degrees of ureter and stent blockage. METHODS: Numerical simulations based on computational fluid dynamics (CFD) were used to quantify urine flow behavior in stented ureters, in the presence of extrinsic ureteral obstruction (EUO) and stent occlusions. Two stented ureter configurations were considered, one with circumferential occlusion of the ureter and the second with pressure on one side of the ureter wall. The pressure within the renal unit for different degrees of ureter closure and stent lumen occlusion was determined systematically. Onset of stent failure and the distribution of urine flow between stent and ureter lumina were determined. RESULTS: In the case of EUO completely encircling the ureter, causing 100% obstruction of the ureter lumen, pressure in the renal unit is essentially unaffected until the stent lumen reaches ~ 90% occlusion, and fails only with > 95% occlusion. Occlusions of 50% in stent side holes in the vicinity of the EUO only alter local flow patterns but have no significant influence on renal unit pressure. For EUO deforming and compressing the ureter from one side, with ~ 50% reduction in ureter lumen, urine drainage proceeds with negligible increase in renal pressure even with 100% occlusion in the stent lumen. CONCLUSION: CFD simulations show that stent failure under EUO tends to occur suddenly, only when both ureter and stent lumina become almost fully blocked.

A deuterium MAS NMR study of the local mobility of dissolved methionine and di-alanine at the inner surface of SBA-15.

The dynamic behavior of guest molecules that are dissolved in water inside the pores of mesoporous materials is important in many fields of research and applications. We demonstrate the exchange dynamics of methionine and dipeptides of alanine inside the pores of SBA-15 by using (1)H and (2)H MAS NMR. These guest molecules may experience intramolecular motion as well as the exchange process. Our results present the rate constants of this exchange process at different hydration levels and sample temperatures, and indicate that these molecules have backbone binding to the silanol sites on the SBA-15 surface similar to alanine (through their N terminus), but show specific intramolecular mobility during the exchange process.

A dynamic magic angle spinning NMR study of the local mobility of alanine in an aqueous environment at the inner surface of mesoporous materials.

Dynamic deuterium magic angle spinning NMR has been applied to study the slow motion of small molecules close to a silica surface. In particular, alanine-d(3) molecules dissolved in an aqueous solution were loaded into the pores of the mesoporous materials SBA-15 and MCM-41. Deuterium spectra were measured as a function of the water content of these materials and the temperature. From the analysis of these spectra and the corresponding proton spectra, using a simple molecular exchange model, relatively slow desorption rates of the binding of alanine to the inner pore surface were obtained and were correlated with the low proton concentrations at the pore surfaces.

Molecular level characterization of the inorganic-bioorganic interface by solid state NMR: alanine on a silica surface, a case study.

The molecular interface between bioorganics and inorganics plays a key role in diverse scientific and technological research areas including nanoelectronics, biomimetics, biomineralization, and medical applications such as drug delivery systems and implant coatings. However, the physical/chemical basis of recognition of inorganic surfaces by biomolecules remains unclear. The molecular level elucidation of specific interfacial interactions and the structural and dynamical state of the surface bound molecules is of prime scientific importance. In this study, we demonstrate the ability of solid state NMR methods to accomplish these goals. L-[1-(13)C,(15)N]Alanine loaded onto SBA-15 mesoporous silica with a high surface area served as a model system. The interacting alanine moiety was identified as the -NH(3)(+) functional group by (15)N{(1)H}SLF NMR. (29)Si{(15)N} and (15)N{(29)Si}REDOR NMR revealed intermolecular interactions between the alanine -NH(3)(+) and three to four surface Si species, predominantly Q(3), with similar internuclear N...Si distances of 4.0-4.2 A. Distinct dynamic states of the adsorbed biomolecules were identified by (15)N{(13)C}REDOR NMR, indicating both bound and free alanine populations, depending on hydration level and temperature. In the bound populations, the -NH(3)(+) group is surface anchored while the free carboxylate end undergoes librations, implying the carboxylate has small or no contributions to surface binding. When surface water clusters grow bigger with increased hydration, the libration amplitude of the carboxyl end amplifies, until onset of dissolution occurs. Our measurements provide the first direct, comprehensive, molecular-level identification of the bioorganic-inorganic interface, showing binding functional groups, geometric constraints, stoichiometry, and dynamics, both for the adsorbed amino acid and the silica surface.

Magnetic resonance imaging and quantitative analysis of particle deposition in porous media.

Measurements of particle deposition and mobilization in water-saturated porous columns were performed using nuclear magnetic resonance imaging (MRI). The use of MRI enabled the acquisition of detailed, noninvasive measurements that quantify spatial and temporal evolution of particle transport patterns and porosity changes due to particle deposition. Measurements indicate that for the considered particle sizes and flow conditions significant particle deposition occurs at some distance into the column. Because identification of unique parametrizations for processes of particle straining, deposition, and detachment is complex and nonunique, a simple phenomenological model of particle deposition and porosity reduction is suggested. This model captures the essential features of the experimental measurements on spatial and temporal flow and deposition patterns.