Acidity: A Key Parameter in Zeolite-Templated Carbon Formation.

This work reveals the crucial role of zeolite acidity in the synthesis of zeolite-templated carbons (ZTCs). While textural and chemical properties appear to be independent from acidity at a given synthesis temperature, the spin concentration in hybrid materials appears to be strongly impacted by the zeolite acid site concentration. The electrical conductivity of the hybrids and resulting ZTCs are closely related to the spin concentration in the hybrid materials. The amount of zeolite acid sites hence fundamentally impacts the electrical conductivity of the samples that spans over a range of four magnitudes. Electrical conductivity reveals as key parameter to describe the quality of ZTCs.

Can We Form Mesoporous Zeolites by Steam Assisted Crystallization of MCM-41?

The possibility of crystallizing silicalite-1 (MFI) from the pore walls of as-synthesized MCM-41 via steam-assisted crystallization (SAC) was thoroughly investigated. A kinetic study was conducted through the impregnation of as-synthesized MCM-41 with the structure-directing agent tetrapropyl-ammonium hydroxide (TPAOH). Materials obtained after different SAC treatment times (1−288 h) were characterized by XRD, nitrogen physisorption at 77 K, TGA/DTA, and SEM. The achieved results allowed us to conclude that during SAC treatment, rapid destruction of the hexagonal mesophase occurs with the enlargement of mesopores, probably by their coalescence, until achieving non-porous amorphous silica. Only thereafter is the crystallization of the MFI phase evidenced through the development of micron-sized (>10 µm) MFI structured crystals. This study suggests the probable practical impossibility of even partial crystallization of the pore walls of mesoporous materials by SAC.

The Energetics of Surfactant-Templating of Zeolites.

Mesoporosity can be conveniently introduced into zeolites by treating them in basic surfactant solutions. The apparent activation energy involved in the formation of mesopores in USY by surfactant-templating was determined using a combination of in situ synchrotron X-ray diffraction and ex situ gas adsorption. Additionally, techniques such as pH measurement and thermogravimetry/differential thermal analysis were employed to determine OH- evolution and cetyltrimethylammonium ion (CTA+ ) uptake during the development of mesoporosity, thereby providing information about the different steps involved. The combination of both in situ and ex situ techniques has allowed determination of the apparent activation energies of the different processes involved in the mesostructuring of USY zeolites for the first time. Apparent activation energies are of the same order of magnitude (30-65 kJ mol-1 ) as those involved in the crystallization of zeolites. Hence, important mechanistic insight into the surfactant-templating method was obtained.

Sentinel-Lymphknoten-Biopsie des Melanoms mittels Indocyaningrün und "FOVIS"-System.

HINTERGRUND: Der Nachweis metastatischer Infiltrate im Sentinel-Lymphkoten (SLN) gilt als wesentlicher prognostischer Faktor des Melanoms. Alternativ zur Farbstoffmethode mit Patentblau zum Goldstandard der SLN-Biopsie (SLNB) mittels Radiokolloid wird die fluoreszenzoptische Darstellung mit Hilfe von Indocyaningrün (ICG) und Nahinfrarot (NIR)-Kamerasystem kommuniziert. Im Vergleich zur konventionellen Methode wurde die Wertigkeit des ICG-/NIR-Verfahrens in Abhängigkeit vom Body-Mass-Index (BMI) des Patienten und der Konzentration von ICG bezüglich der Visualisierung des Lymphabstroms und des SLNs untersucht. PATIENTEN UND METHODIK: An zehn Patienten wurde die SLNB mittels Technetium-99m, Patentblau und ICG durchgeführt. Die Fluoreszenz-Darstellung von Lymphbahnen und SLN erfolgte in Echtzeit mittels der NIR-Kameratechnik "FOVIS". Je nach erzielter Bildqualität wurde ICG in einer Dosis von 0,25 mg bis 2,5 mg intrakutan appliziert. ERGEBNISSE: Neun der zehn SLN wurden fluoreszenzoptisch identifiziert (90 %), alle zehn radioaktiv (100 %), nur acht (80 %) mittels ICG-Grünfärbung bzw. Patenblau-Markierung. Transdermal wurde ein SLN dargestellt (10 %). In Korrelation zum BMI waren höhere ICG-Mengen, bis zu 2,5 mg intrakutan absolut, in der Darstellung der Lymphbahnen von Vorteil. SCHLUSSFOLGERUNGEN: Die SLN-Fluoreszenzmarkierung mit dem ICG/NIR-Kamera-System "FOVIS" stellt eine sichere Alternative zur Farbstoffmethode mit Patentblau ergänzend zur Radiokolloidmethode mit Technetium-99m dar. Weitere Studien zur optimalen Dosierung von ICG und transdermalen Bildgebung in Relation zum BMI sind notwendig.

Indocyanine green-assisted sentinel lymph node biopsy in melanoma using the "FOVIS" system.

BACKGROUND: Metastatic involvement of the sentinel lymph node (SLN) represents a key prognostic factor in melanoma. The combined use of a radiocolloid (technetium-99m) and blue dye is the gold standard in sentinel lymph node biopsy (SLNB). In this context, near-infrared (NIR) fluorescence imaging with indocyanine green (ICG) has been suggested as an alternative. The objective of the present study was to examine the potential advantages of fluorescence-guided SLNB - compared to the conventional method - with respect to the visualization of lymphatic drainage pathways and the SLN. Particular focus was on the impact of the ICG dose used and the body mass index (BMI). PATIENTS AND METHODS: The study included ten patients who underwent the SLNB procedure using technetium-99m, blue dye, and ICG. Real-time fluorescence imaging of lymphatic drainage pathways and the SLN was done using the "FOVIS"-NIR system. Depending on the quality of the images achieved, ICG was intradermally administered at a dose ranging from 0.25 to 2.5 mg. RESULTS: Nine SLNs were identified by fluorescence (90 %); (100 %) ten, by gamma probe; eight (80 %), by ICG or blue dye. Transdermal SLN detection was possible in one case (10 %). In correlation to the BMI, higher intradermal ICG doses - up to 2.5 mg overall - proved to be advantageous in the visualization of lymphatic vessels. CONCLUSIONS: Supplementing the technetium-99m method, fluorescence SLNB using ICG and the "FOVIS"-NIR system is a safe alternative to the blue-dye technique. Further studies on the optimal ICG dose and transdermal imaging in correlation to the BMI are required.

Mesoporous alumina from colloidal biotemplating of Al clusters.

A simple and green synthesis route was disclosed for the achievement of mesoporous alumina microparticles employing polysaccharide nanoparticles (α-chitin nanorods) as templates. Pore textures can be tuned by the cationic alumina precursor. Compared to small cations, the use of Al13 and Al30 oxo-hydroxo clusters leads to better defined and elongated mesopores. Electron microscopy and spectroscopic ((13) C, (27) Al NMR, XPS) measurements demonstrated that this is related to the effective coating of α-chitin nanorods by these pre-condensed colloids.

Ordered mesoporous ZSM-5 employing an imidazolium-based ionic liquid.

Hierarchically porous ZSM-5 was achieved by using a simple bottom-up strategy combining zeolite seeds with imidazolium-based ionic liquids. The bimodal ZSM-5 with hexagonal arranged mesopores (3 nm) shows important activity in the acid catalysis of bulky compounds relative to conventional ZSM-5.

Gas Porosimetry by Gas Adsorption as an Efficient Tool for the Assessment of the Shaping Effect in Commercial Zeolites.

A set of three commercial zeolites (13X, 5A, and 4A) of two distinct shapes have been characterized: (i) pure zeolite powders and (ii) extruded spherical beads composed of pure zeolite powders and an unknown amount of binder used during their preparation process. The coupling of gas porosimetry experiments using argon at 87 K and CO2 at 273 K allowed determining both the amount of the binder and its effect on adsorption properties. It was evidenced that the beads contain approximately 25 wt% of binder. Moreover, from CO2 adsorption experiments at 273 K, it could be inferred that the binder present in both 13X and 5A zeolites does not interact with the probe molecule. However, for the 4A zeolite, pore filling pressures were shifted and strong interaction with CO2 was observed leading to irreversible adsorption of the probe. These results have been compared to XRD, IR spectroscopy, and ICP-AES analysis. The effect of the binder in shaped zeolite bodies can thus have a crucial impact on applications in adsorption and catalysis.

Functionalized inorganic monolithic microreactors for high productivity in fine chemicals catalytic synthesis.

Highly productive: Grafted monolith silica skeleton microreactors process bulky molecules more efficiently than a batch mode reactor. This efficiency is due to a higher contact area, shorter diffusion path, and lower inhibition by products in the thin monolith skeleton. These materials provide a new approach in the field of heterogeneous catalysis for the synthesis of fine chemicals.

Selective hydrogenation over Pd nanoparticles supported on a pore-flow-through silica monolith microreactor with hierarchical porosity.

Well-dispersed Pd nanoparticles have been synthesized inside the mesoporosity of a silica monolith featuring hierarchical porosity of homogeneous interconnected macropores (4 microns) and mesopores (11 nm). These monoliths have been implemented as microreactors for selective hydrogenation reactions. Conversion and selectivity can be tuned by adjusting the flow rates of hydrogen and substrates. In the selective hydrogenation of cyclooctadiene, a conversion of 95% and a selectivity of 90% in the monohydrogenated product, constant over a period of 70 h, have been reached. These figures correspond to a productivity of 4.2 mmol s(-1) g(-1)(MonoSil) (or 0.32 mol s(-1) g(-1)(Pd)). In the stereoselective hydrogenation of 3-hexyn-1-ol a constant conversion of 85% was observed, with however moderate selectivity into the cis isomer, over a test period of 7 h. These results open the route to the synthesis of important chemicals and intermediates via safe and green processes.

Challenges and Strategies in the Synthesis of Mesoporous Alumina Powders and Hierarchical Alumina Monoliths.

A new rapid, very simple and one-step sol-gel strategy for the large-scale preparation of highly porous γ-Al2O3 is presented. The resulting mesoporous alumina materials feature high surface areas (400 m² g-1), large pore volumes (0.8 mL g-1) and the γ-Al2O3 phase is obtained at low temperature (500 °C). The main advantages and drawbacks of different preparations of mesoporous alumina materials exhibiting high specific surface areas and large pore volumes such as surfactant-nanostructured alumina, sol-gel methods and hierarchically macro-/mesoporous alumina monoliths have been analyzed and compared. The most reproducible synthesis of mesoporous alumina are given. Evaporation-Induced Self-Assembly (EISA) is the sole method to lead to nanostructured mesoporous alumina by direct templating, but it is a difficult method to scale-up. Alumina featuring macro- and mesoporosity in monolithic shape is a very promising material for in flow applications; an optimized synthesis is described.

In situ synthesis of Cu-BTC (HKUST-1) in macro-/mesoporous silica monoliths for continuous flow catalysis.

The metal-organic framework Cu-BTC has been successfully synthesized as nanoparticles inside the mesopores of silica monoliths featuring a homogeneous macropore network enabling the use of Cu-BTC for continuous flow applications in liquid phase with low pressure drop. High productivity was reached with this catalyst for the Friedländer reaction.

Efficient mesoporous silica-titania catalysts from colloidal self-assembly.

Mesoporous silica-titania materials of tunable composition and texture, which present a high catalytic activity in the mild oxidation of sulfur compounds, have been obtained by combining the spray-drying process with the colloidal self-assembly of α-chitin nanorods (biopolymer acting as a template) and organometallic oligomers.