A novel method for tailoring the pore-opening size of MCM-41 materials

A novel pore tailoring method is proposed by which the pore-opening sizes of MCM-41 materials can be finely tuned without significant loss in pore volume and surface area.

2-pyrazinylnitrene and 4-pyrimidylnitrene. Ring expansion to 1,3,5-triazacyclohepta-1,2,4,6-tetraene and ring opening to (2-isocyanovinyl)carbodiimide

Tetrazolo[1,5-a]pyrazine/2-azidopyrazine 9T/9A undergo photolysis in Ar matrix at cryogenic temperatures to yield 1,3,5-triazacyclohepta-1,2,4,6-tetraene 21 as the first observable intermediate, and 1-cyanoimidazole 11 and (2-isocyanovinyl)carbodiimide 22 as the final products. The latter tautomerizes to 2-(isocyanovinyl)cyanamide 23 on warming to 40 K. The same intermediate 21 and the same final products are obtained on matrix photolysis of the isomeric tetrazolo[1,5-c]pyrimidine/4-azidopyrimidine 24T/24A. These photolysis results as well as those of the previously reported thermal ring contraction of N-15-labeled 2-pyrazinyl- and 4-pyrimidylnitrenes to 1-cyanoimidazoles can all be rationalized in terms of selective ring opening of 21 or nitrine 10 to a nitrile ylide zwitterion 28 prior to formation of the final products, 11 and 22. The results are supported by high-level ab initio and DFT calculations (CASPT2-CASSCF(6,6), G3(MP2), and B3LYP/6-31+G*) of the energies and IR spectra of the intermediates and products.

3-pyridylcarbene and 3-pyridylnitrene: Ring opening to nitrile ylides

Photolysis of 3-pyridyldiazomethane in an Ar matrix at 7-10 K gives 3-pyridylcarbene. Further photolysis causes ring opening to nitrile ylide 26 (formonitrile pent-2-en-4-ynylide) as the major reaction together with a minor amount of ring expansion to 1-azacyclohepta-1,3,4,6-tetraene, 27. Matrix photolysis of 3-azidopyridine leads to ring opening to formonitrile N-cyanovinylmethylide, 33.

2-quinolyl- and 1-isoquinolylnitrenes: Ring expansion and ring opening in heteroarylnitrenes

Argon matrix photolysis of tetrazolo[1,5-a]quinoline 8 and tetrazolo[5,1-a]isoquinoline 7 causes nitrogen elimination and ring expansion to 1,3-diazabenzo[d]cyclohepta-1,2,4,6-tetraene 13. The photolysis of tetrazolo[5,1-a]isoquinoline 7 also causes ring opening to o-cyanophenylketenimine 22. Mechanisms of ring opening of heteroarylnitrenes are discussed.

Opening windows into the mind: mothers' preferences for mental state explanations and children's theory of mind

A new questionnaire, the Maternal Mental State Input Inventory (MMSII) was created to measure mothers' preferences for introducing and elaborating on mental states in conversation with their young children. In two studies, the questionnaire was given to mothers of young children, and the children's theory of mind (ToM) development was assessed with standard tasks. In both studies, the questionnaire exhibited good internal reliability, and significant correlations emerged between mothers' self-reported preferences for elaborated, explanatory talk about the mental states and children's theory of mind performance. Further, mothers' conversational preferences, as measured by the MMSII, were the best predictors of children's theory of mind development when relevant control variables were included in the analyses. These results converge with naturalistic observational research that has demonstrated links between mothers' conversational styles and their children's theory of mind. They go further in suggesting that mothers' tendencies toward elaborated, explanatory talk about a range of mental states is particularly beneficial to children's theory of mind development. (C) 2003 Elsevier Inc. All rights reserved.

K-Ar and 40Ar/39Ar ages of dikes emplaced in the onshore basement of the Santos Basin, Resende area, SE Brazil: implications for the South Atlantic opening and tertiary reactivation

New K-Ar and Ar-40/Ar-39 data of tholeiitic and alkaline dike swarms from the onshore basement of the Santos Basin (SE Brazil) reveal Mesozoic and Tertiary magmatic pulses. The tholeiitic rocks (basalt, dolerite, and microgabbro) display high TiO2 contents (average 3.65 wt%) and comprise two magmatic groups. The NW-oriented samples of Group A have (La/Yb)N ratios between 15 and 32.3 and range in age from 192.9 +/- 2.2 to 160.9 +/- 1.9 Ma. The NNW-NNE Group B samples, with (La/Yb)(N) ratios between 7 and 16, range from 148.3 +/- 3 to 133.9 +/- 0.5 Ma. The alkaline rocks (syenite, trachyte, phonolite, alkaline basalts, and lamprophyre) display intermediate-K contents and comprise dikes, plugs, and stocks. Ages of approximately 82 Ma were obtained for the lamprophyre dikes, 70 Ma for the syenite plutons, and 64-59 Ma for felsic dikes. Because Jurassic-Early Cretaceous basic dikes have not been reported in SE Brazil, we might speculate that, during the emplacement of Group A dikes, extensional stresses were active in the region before the opening of the south Atlantic Ocean and coeval with the Karoo magmatism described in South Africa. Group B dikes yield ages compatible with those obtained for Serra Geral and Ponta Grossa magmatism in the Parana Basin and are directly related to the breakup of western Gondwana. Alkaline magmatism is associated with several tectonic episodes that postdate the opening of the Atlantic Ocean and related to the upwelling of the Trindade plume and the generation of Tertiary basins southeast of Brazil. In the studied region, alkaline magmatism can be subdivided in two episodes: the first one represented by lamprophyre dykes of approximately 82 Ma and the second comprised of felsic alkaline stocks of approximately 70 Ma and associated dikes ranging from 64 to 59 Ma. (c) 2005 Elsevier Ltd. All rights reserved.

Biocompatible properties of surgical mesh using an animal model

To study the biocompatibility of surgical meshes for use in pelvic reconstructive surgery using an animal model. Eight different types of mesh: Atrium, Dexon, Gynemesh, IVS tape, Prolene, SPARC tape, TVT tape and Vypro II, were implanted into the abdominal walls of rats for 3 months' duration. Explanted meshes were assessed, using light microscopy, for parameters of rejection and incorporation. Type 1 (Atrium, Gynemesh, Prolene, SPARC and TVT) and type 3 (Vypro II, Dexon and IVS) meshes demonstrated different biocompatible properties. Inflammatory cellular response and fibrosis at the interface of mesh and host tissue was most marked with Vypro II and IVS. All type 1 meshes displayed similar cellular responses despite markedly different mesh architecture. The inflammatory response and fibrous reaction in the non-absorbable type 3 meshes tested (IVS and Vypro II) was more marked than the type 1 meshes. The increased inflammatory and fibrotic response may be because of the multifilamentous polypropylene components of these meshes. Material and filament composition of mesh is the main factor in determining cellular response.