Deep Anterior Lamellar Keratoplasty versus Penetrating Keratoplasty for Macular Corneal Dystrophy: A Randomized Trial

Purpose: To compare outcomes of big-bubble deep anterior lamellar keratoplasty (DALK) and penetrating keratoplasty (PK) for macular corneal dystrophy. Design: Prospective, randomized, interventional case series. Methods: Setting: Single hospital. Patients: Eighty-two eyes of 54 patients requiring keratoplasty for the treatment of macular corneal dystrophy without endothelial involvement were included. Main outcome measures: Operative complications, uncorrected visual acuity, best-corrected visual acuity, contrast sensitivity function, higher-order aberrations, and endothelial cell density were evaluated. Results: The DALK and PK group consisted of 35 and 41 eyes, respectively. Best-corrected visual acuity after surgery was 20/40 or better 68.5% and 70.7% of the eyes in the DALK and PK groups, respectively (P > .05). No statistically significant differences between groups were found in contrast sensitivity function with and without glare for any spatial frequency (P > .05). Significantly higher levels of higher-order aberrations were found in the DALK group (P < .01). In both groups, a progressive and statistically significant reduction in endothelial cell density was found (P < .01). At the last follow-up, the mean endothelial cell loss was 18.1% and 26.9% in DALK and PK groups, respectively (P = .03). Graft rejection episodes were seen in 5 eyes (12.1%) in the PK group, and regrafting was necessary in 3 eyes (7.3%). Recurrence of the disease was documented in 5.7% and 4.8% of the eyes in the DALK and PK groups, respectively. Conclusions: Deep anterior lamellar keratoplasty with the big-bubble technique provided comparable visual and optical results as PK and resulted in less endothelial damage, as well as eliminating endothelial rejection in macular corneal dystrophy. Deep anterior lamellar keratoplasty surgery is a viable option for macular corneal dystrophy without endothelial involvement.

Water adsorption in hydrophilic zeolites: experiment and simulation

We have measured experimental adsorption isotherms of water in zeolite LTA4A, and studied the regeneration process by performing subsequent adsorption cycles after degassing at different temperatures. We observed incomplete desorption at low temperatures, and cation rearrangement at successive adsorption cycles. We also developed a new molecular simulation force field able to reproduce experimental adsorption isotherms in the range of temperatures between 273 K and 374 K. Small deviations observed at high pressures are attributed to the change in the water dipole moment at high loadings. The force field correctly describes the preferential adsorption sites of water at different pressures. We tested the influence of the zeolite structure, framework flexibility, and cation mobility when considering adsorption and diffusion of water. Finally, we performed checks on force field transferability between different hydrophilic zeolite types, concluding that classical, non-polarizable water force fields are not transferable.

Abatement of hydrocarbons by acid ZSM-5 and BETA zeolites under cold-start conditions

Simulated cold-start tests have been carried out to evaluate the performance of H-ZSM-5 and H-BETA zeolites as hydrocarbon traps under simulated gasoline car exhaust gases, paying special attention to the effect of water on their behaviour. It is concluded that the hydrothermal treatment of the zeolites in the acidic form contributes to the better performance of these materials as hydrocarbon traps since the stabilization of the zeolites takes place. Moreover, the decrease of the surface acidity of the zeolites results in an increase of the Si/Al ratio, which contributes to the decrease of the water affinity for adsorption sites. Thus, the competition with hydrocarbon molecules in the exhaust for the adsorption sites is reduced which increases their trap efficiency. The stabilized H-ZSM-5 is the zeolite that showed the best performance with a propene offset temperature of 240 °C, which should be high enough for the three-way catalyst to carry out its role as catalytic converter.

Investigation of Pd nanoparticles supported on zeolites for hydrogen production from formic acid dehydrogenation

Catalysts based on palladium nanoparticles supported on different zeolites (BETA, ZSM-5 and Y) were prepared and their catalytic performance in formic acid dehydrogenation was studied. The effects of the zeolite structure and porous texture on the catalytic activity were investigated by comparing the behavior of these samples. The results revealed that the samples based on BETA zeolite are promising catalysts for this application.

Evidence of Intracrystalline Mesostructured Porosity in Zeolites by Advanced Gas Sorption, Electron Tomography and Rotation Electron Diffraction

The small size of micropores (typically <1 nm) in zeolites causes slow diffusion of reactant and product molecules in and out of the pores and negatively impacts the product selectivity of zeolite based catalysts, for example, fluid catalytic cracking (FCC) catalysts. Size-tailored mesoporosity was introduced into commercial zeolite Y crystals by a simple surfactant-templating post-synthetic mesostructuring process. The resulting mesoporous zeolite Y showed significantly improved product selectivity in both laboratory testing and refinery trials. Advanced characterization techniques such as electron tomography, three-dimensional rotation electron diffraction, and high resolution gas adsorption coupled with hysteresis scanning and density functional theory, unambiguously revealed the intracystalline nature and connectivity of the introduced mesopores. They can be considered as molecular highways that help reactant and product molecules diffuse quickly to and away from the catalytically active sites within the zeolite crystals and, thus, shift the selectivity to favor the production of more of the valuable liquid fuels at reduced yields of coke and unconverted feed.

Insights into the Active Species of Nanoparticle-Functionalized Hierarchical Zeolites in Alkylation Reactions

Supported iron oxide nanoparticles have been incorporated onto hierarchical zeolites by microwave-assisted impregnation and mechanochemical grinding. Nanoparticle-functionalised porous zeolites were characterised by a number of analytical techniques such as XRD, N2 physisorption, TEM, and surface acidity measurements. The catalytic activities of the synthesised nanomaterials were investigated in an alkylation reaction. The results pointed to different species with varying acidity and accessibility in the materials, which provided essentially different catalytic activities in the alkylation of toluene with benzyl chloride under microwave irradiation, selected as the test reaction.

Mesostructured zeolites: bridging the gap between zeolites and MCM-41

Surfactant-templating is one of the most versatile and useful techniques to implement mesoporous systems into solid materials. Various strategies based on various interactions between surfactants and solid precursors have been explored to produce new structures. Zeolites are invaluable as size- and shape-selective solid acid catalysts. Nevertheless, their micropores impose limitations on the mass transport of bulky feed and/or product molecules. Many studies have attempted to address this by utilizing surfactant-assisting technology to alleviate the diffusion constraints. However, most efforts have failed due to micro/mesopore phase separation. Recently, a new technique combining the uses of cationic surfactants and mild basic solutions was introduced to synthesise mesostructured zeolites. These materials sustain the unique characteristics of zeolites (i.e., strong acidity, crystallinity, microporosity, and hydrothermal stability), including tunable mesopore sizes and degrees of mesoporosity. The mesostructured zeolites are now commercially available through Rive Technology, and show superior performance in VGO cracking. This feature article provides an overview of recent explorations in the introduction of mesoporosity into zeolites using surfactant-templating techniques. Various porous materials, preparation methods, physical and catalytic properties of mesostructured zeolites will be discussed.

The role of mesoporosity and Si/Al ratio in the catalytic etherification of glycerol with benzyl alcohol using ZSM-5 zeolites

A comparative study of the influence of three different acid solids as catalysts (conventional zeolites Z15c with Si/Al = 19.5 and Z40c with Si/Al = 48.2, and a hierarchical zeolite Z40c-H with Si/Al = 50.0) for the etherification of glycerol with benzyl alcohol was performed. The catalytic activity and selectivity of these zeolites was elucidated at different catalyst contents. Three different ethers (3-benzyloxy-1,2-propanediol, which is a mono-benzyl-glycerol ether (MBG) and 1,3-dibenzyloxy-2-propanol, which is a di-benzyl-glycerol ether (DBG) and dibenzyl ether (DBz) were identified as the main products. MBG was the major product of the reaction catalyzed by the microporous Z15c zeolite with low Si/Al molar ratio, whereas DBG was formed in higher yield with the use of microporous Z40c and hierarchical Z40c-H zeolites, both of them having a similar high Si/Al molar ratio (≈50). MBG is a value-added product and it is obtained with good yield and selectivity when using the conventional zeolite Z15c as a catalyst. Under the best conditions tested, i.e., 25 mg of catalyst for 8 h at 120 °C, a 62% of conversion was obtained without the need of solvent, with an excellent 84% selectivity toward the MBG and no formation of DBz.

Realizing the Commercial Potential of Hierarchical Zeolites: New Opportunities in Catalytic Cracking

Many approaches to mesoporous zeolites have been reported. The preparation of mesoporous zeolite Y, as the most widely used zeolite in catalysis, its properties, and its application in fluid catalytic cracking (FCC) and hydrocracking are reviewed. Finally, the scale-up and use of mesostrutured zeolite Y on an industrial scale are described, as the first commercial application of hierarchical zeolites.

Material demands for storage technologies in a hydrogen economy

A hydrogen economy is needed, in order to resolve current environmental and energy-related problems. For the introduction of hydrogen as an important energy vector, sophisticated materials are required. This paper provides a brief overview of the subject, with a focus on hydrogen storage technologies for mobile applications. The unique properties of hydrogen are addressed, from which its advantages and challenges can be derived. Different hydrogen storage technologies are described and evaluated, including compression, liquefaction, and metal hydrides, as well as porous materials. This latter class of materials is outlined in more detail, explaining the physisorption interaction which leads to the adsorption of hydrogen molecules and discussing the material characteristics which are required for hydrogen storage application. Finally, a short survey of different porous materials is given which are currently investigated for hydrogen storage, including zeolites, metal organic frameworks (MOFs), covalent organic frameworks (COFs), porous polymers, aerogels, boron nitride materials, and activated carbon materials.

Tailoring the surface chemistry of zeolite templated carbon by electrochemical methods

One option to optimize carbon materials for supercapacitor applications is the generation of surface functional groups that contribute to the pseudocapacitance without losing the designed physical properties. This requires suitable functionalization techniques able to selectively introduce a given amount of electroactive oxygen groups. In this work, the influence of the chemical and electrochemical oxidation methods, on the chemical and physical properties of a zeolite templated carbon (ZTC), as a model carbon material, have been studied and compared. Although both oxidation methods generally produce a loss of the original ZTC physical properties with increasing amount of oxidation, the electrochemical method shows much better controllability and, unlike chemical treatments, enables the generation of a large number of oxygen groups (O = 11000- 3300 μmol/g), with a higher proportion of active functionalities, while retaining a high surface area (ranging between 1900-3500 m2/g), a high microporosity and an ordered 3-D structure.

Ordered porous nanomaterials: the merit of small

This paper will introduce the reader to some of the “classical” and “new” families of ordered porous materials which have arisen throughout the past decades and/or years. From what is perhaps the best-known family of zeolites, which even now to this day is under constant research, to the exciting new family of hierarchical porous materials, the number of strategies, structures, porous textures, and potential applications grows with every passing day. We will attempt to put these new families into perspective from a synthetic and applied point of view in order to give the reader as broad a perspective as possible into these exciting materials.

Desilication of TS-1 zeolite for the oxidation of bulky molecules

A series of modified TS-1 samples have been produced by desilication of the original TS-1 (4 wt.% Ti) using a chemical treatment with NaOH. Desilicated TS-1 zeolites exhibit a large BET surface area together with a well-developed mesoporosity. The hierarchical catalysts from desilication of TS-1 zeolite show a good catalytic activity for the oxidation of small molecules and a significantly higher activity for the oxidation of bulky molecules.

Phagocytosis of Photoreceptor Outer Segments by Transplanted Human Neural Stem Cells as a Neuroprotective Mechanism in Retinal Degeneration

Purpose. Transplantation of human central nervous system stem cells (HuCNS-SC) into the subretinal space of Royal College of Surgeons (RCS) rats preserves photoreceptors and visual function. To explore possible mechanism(s) of action underlying this neuroprotective effect, we performed a detailed morphologic and ultrastructure analysis of HuCNS-SC transplanted retinas. Methods. The HuCNS-SC were transplanted into the subretinal space of RCS rats. Histologic examination of the transplanted retinas was performed by light and electron microscopy. Areas of the retina adjacent to HuCNS-SC graft (treated regions) were analyzed and compared to control sections obtained from the same retina, but distant from the transplant site (untreated regions). Results. The HuCNS-SC were detected as a layer of STEM 121 immunopositive cells in the subretinal space. In treated regions, preserved photoreceptor nuclei, as well as inner and outer segments were identified readily. In contrast, classic signs of degeneration were observed in the untreated regions. Interestingly, detailed ultrastructure analysis revealed a striking preservation of the photoreceptor–bipolar–horizontal cell synaptic contacts in the outer plexiform layer (OPL) of treated areas, in stark contrast with untreated areas. Finally, the presence of phagosomes and vesicles exhibiting the lamellar structure of outer segments also was detected within the cytosol of HuCNS-SC, indicating that these cells have phagocytic capacity in vivo. Conclusions. This study reveals the novel finding that preservation of specialized synaptic contacts between photoreceptors and second order neurons, as well as phagocytosis of photoreceptor outer segments, are potential mechanism(s) of HuCNS-SC transplantation, mediating functional rescue in retinal degeneration.

Total oxidation of naphthalene using palladium nanoparticles supported on BETA, ZSM-5, SAPO-5 and alumina powders

A range of catalysts based on Pd nanoparticles supported on inorganic supports such as BETA and ZSM-5 zeolites, a silicoaluminophosphate molecular sieve (SAPO-5) and γ-alumina as a standard support have been tested for the total oxidation of naphthalene (100 ppm, total flow 50 ml/min) showing a conversion to carbon dioxide of 100% between 165 and 180 °C for all the analysed catalysts. From the combined use of zeolites with PVP polymer protected Pd based nanoparticles, enhanced properties have been found for the total abatement of naphthalene in contrast with other kinds of catalysts. A Pd/BETA catalyst has been demonstrated to have excellent activity, with a high degree of stability, as shown by time on line experiments maintaining 100% conversion to CO2 during the 48 h tested.