•Phosphate treatments of MTW/Al2O3 increased selectivity to gasoline up to 97%.•H3PO4 caused conversion of the γ-Al2O3 binding matrix to crystalline tridymite-AlPO4.•Interaction of P with zeolite framework Al species observed, confirming Si-O-Al-O-P bonds.•Si-O-Al-O-P bond formation is a major effect from phosphate treatment.•10%P from H3PO4 on 80/20 MTW/Al2O3 as effective as SPA in oligomerization to gasoline.

Since the discovery of titanium silicalite more than 30 years ago, framework metal-containing zeotype materials have become an important class of catalyst, finding application in several industrial processes. Incorporation of cations of titanium, tin, iron, and other elements into zeotype frameworks (and also into ordered mesoporous materials) has led to both scientific progress and engineering innovations in catalysis. As a result of these developments, framework metal-containing zeotype materials have been implemented in the preceding decade in new commercial, by-product-free green processes, which have improved sustainability in the chemical industry. Based on a comprehensive analysis of the recent literature including patents, this review is a summary of the current knowledge of the science and technology of framework metal-containing zeotype materials. The synthesis of these materials is summarized, followed by an account of state-of-the-art characterization results. The key catalytic chemistries, which can be classified into oxidation reactions such as olefin epoxidation, aromatic hydroxylation and ammoximation, and weak Lewis acid-catalyzed reactions, are discussed. Mechanisms proposed for these transformations are reviewed, together with the theoretical and modeling tools applied in this context. An overview of the technologies associated with the use of framework metal-containing zeotype materials demonstrates how these processes are linked with each other through key chemicals involved.

Serum amyloid P component (SAP), a member of the innate immune system, does not penetrate the brain in physiological conditions; however, SAP is a stabilizing component of the amyloid plaques in neurodegenerative diseases. We investigated the cerebrovascular transport of human SAP in animal experiments and in culture blood-brain barrier (BBB) models. After intravenous injection, no SAP could be detected by immunohistochemistry or ELISA in healthy rat brains. Salmonella typhimurium lipopolysaccharide injection increased BBB permeability for SAP and the number of cerebral vessels labeled with fluorescein isothiocyanate (FITC)-SAP in mice. Furthermore, when SAP was injected to the rat hippocampus, a time-dependent decrease in brain concentration was seen demonstrating a rapid SAP efflux transport in vivo. A temperature-dependent bidirectional transport of FITC-SAP was observed in rat brain endothelial monolayers. The permeability coefficient for FITC-SAP was significantly higher in abluminal to luminal (brain to blood) than in the opposite direction. The luminal release of FITC-SAP from loaded endothelial cells was also significantly higher than the abluminal one. Our data indicate the presence of BBB efflux transport mechanisms protecting the brain from SAP penetration. Damaged BBB integrity due to pathological insults may increase brain SAP concentration contributing to development of neurodegenerative diseases.

OBJECTIVE:The pathogenesis of appendicitis remains poorly understood. However, there is increasing evidence of involvement of the enteric nervous system in immune regulation and in inflammatory responses. This study was set up to characterize the status of the enteric nervous system in normal and in inflamed appendixes.METHODS:S100- and 2',2'-cyclic nucleotide 3' phosphodiesterase-positive Schwann cells, synaptophysin, and neuron-specific, enolase-positive nerve fibers and tryptase-positive mast cells were evaluated with immunohistochemical staining in surgically resected appendixes from 20 children with histologically proven acute appendicitis (HA), 10 histologically normal appendixes (HN) from patients with a clinical diagnosis of appendicitis, and 10 normal appendixes from patients undergoing elective abdominal surgery. Immunostained sections were subjected to quantitative image analysis. The number and size of ganglia and the number of nerve fibers, Schwann cells, and mast cells in each tissue compartment was quantitatively or semiquantitatively measured.RESULTS:Increased numbers of fibers, Schwann cells, and enlarged ganglia, widely distributed in the muscularis externa and submucosa, were seen in all HA appendixes and in 4 of 10 HN appendixes. The number and size of ganglia in muscularis externa and in the submucosa of appendixes with HA were significantly greater compared with those in control appendixes (P <.001). A significantly increased number of individually stained nerve fibers and Schwann cells (P <.05) were present in the muscularis externa in HA appendixes compared with control appendixes. Significantly increased numbers of tryptase-positive mast cells (P <.05) were present in the submucosa, muscularis, and especially in the lamina propria in HA specimens, compared with that of control tissue.CONCLUSIONS:The significant increase in neural components and mast cells in acute appendicitis is unlikely to develop during a single acute inflammatory episode. This suggests an underlying chronic abnormality as a secondary reaction to repeated bouts of inflammation, obstruction, or both. These results challenge our current understanding of the pathophysiological processes that give rise to acute appendicitis.

Oxidation of thiophene and its derivatives was studied using hydrogen peroxide (H2O2), t-butyl-hydroperoxide and Ti-Beta redox molecular sieve as selective oxidation catalysts. A new reaction pathway was discovered and investigated using C-13 NMR, GC, GC-MS, HPLC, ion chromatography, and XANES. The thiophene oxidized to thiophene-sesquioxide [3a,4,7,7a-tetrahydro-4,7-epithiobenzo[b]-thiophene 1,1.8-trioxide] and the sesquioxide oxidized mostly to sulfate. 2-Methyl-thiophene and 2,5 dimethylthiophene also oxidized to sulfate and sulfone products. The Benzothiophene oxidation product was sulfone. This proposed new reaction pathway is different from prior literature, which reported the formation of thiophene 1,1-dioxide (sulfone) as a stable oxidation product

Extract Extended abstract of a paper presented at Microscopy and Microanalysis 2007 in Ft. Lauderdale, Florida, USA, August 5 – August 9, 2007

UZM-12 is a microporous crystalline aluminosilicate with ERI topology synthesized via the Charge Density Mismatch approach. The Charge Density Mismatch approach features synthesis from clear aluminosilicate solutions with high organic template content that are subsequently treated with crystallization inducing solutions. The solution containing low amounts of alkali and a higher charge density organic "crystallization" template, yields UZM-12 with Si/Al > 5.5 and nano- to micron-sized crystallites of spherical, plate or rod morphology depending on crystallization template, K+/Al ratio and synthesis conditions. Crystallization templates include the diquat-6, diquat-4, and benzyltrimethylammonium cations. The thermal, steam stability, and acid properties of H-UZM-12 were determined using the combinatorial heptane microreactor.

Extended abstract of a paper presented at MC 2007, 33rd DGE Conference in Saarbrücken, Germany, September 2 – September 7, 2007

Effects of tin incorporation in titanium silicalite-1 (TS-1) on the kinetic modelling of phenol hydroxylation to dihydroxybenzenes with aqueous hydrogen peroxide have been investigated. The modelling of the hydroxylation reaction was from the results of a batch reactor, minimizing mass transfer conditions. The kinetic analysis indicates that under the same reaction conditions, titanium-tin silicalite-1 (Ti-Sn-S-1) gave a higher phenol conversion rate than TS-1. This was attributed to the Sn active sites. Incorporation of tin influences the initiation of intermediate reactions of products with hydrogen peroxide. Tin increases the rate of benzoquinone conversion to tar; however, it does not affect hydroquinone and catechol reactions. A Langmuir–Hinshelwood-type mechanism model was used to fit the proposed phenol hydroxylation and parallel reactions of products with the observed rate data. The intrinsic kinetic constants were found to be proportional to the concentration of reactants and the Ti and Sn active sites. The surface reaction yielded the best fit of the model for reactions in the system. It however failed to predict the outcome of the catechol reaction using TS-1, in which the catechol adsorption on the Ti active site was rate-limiting. The model fitted to the experimental data generated in this study was determined to provide the best values for the kinetic parameters. The effect of temperature on the hydroxylation rate is also documented in further detail.