From Concept to Crystals via Prediction: Multi-Component Organic Cage Pots by Social Self-Sorting.

We describe the a priori computational prediction and realization of multi-component cage pots, starting with molecular predictions based on candidate precursors through to crystal structure prediction and synthesis using robotic screening. The molecules were formed by the social self-sorting of a tri-topic aldehyde with both a tri-topic amine and di-topic amine, without using orthogonal reactivity or precursors of the same topicity. Crystal structure prediction suggested a rich polymorphic landscape, where there was an overall preference for chiral recognition to form heterochiral rather than homochiral packings, with heterochiral pairs being more likely to pack window-to-window to form two-component capsules. These crystal packing preferences were then observed in experimental crystal structures.

Near-Ideal Xylene Selectivity in Adaptive Molecular Pillar[ n]arene Crystals.

The energy-efficient separation of alkylaromatic compounds is a major industrial sustainability challenge. The use of selectively porous extended frameworks, such as zeolites or metal-organic frameworks, is one solution to this problem. Here, we studied a flexible molecular material, perethylated pillar[ n]arene crystals ( n = 5, 6), which can be used to separate C8 alkylaromatic compounds. Pillar[6]arene is shown to separate para-xylene from its structural isomers, meta-xylene and ortho-xylene, with 90% specificity in the solid state. Selectivity is an intrinsic property of the pillar[6]arene host, with the flexible pillar[6]arene cavities adapting during adsorption thus enabling preferential adsorption of para-xylene in the solid state. The flexibility of pillar[6]arene as a solid sorbent is rationalized using molecular conformer searches and crystal structure prediction (CSP) combined with comprehensive characterization by X-ray diffraction and 13C solid-state NMR spectroscopy. The CSP study, which takes into account the structural variability of pillar[6]arene, breaks new ground in its own right and showcases the feasibility of applying CSP methods to understand and ultimately to predict the behavior of soft, adaptive molecular crystals.

Computationally-Guided Synthetic Control over Pore Size in Isostructural Porous Organic Cages.

The physical properties of 3-D porous solids are defined by their molecular geometry. Hence, precise control of pore size, pore shape, and pore connectivity are needed to tailor them for specific applications. However, for porous molecular crystals, the modification of pore size by adding pore-blocking groups can also affect crystal packing in an unpredictable way. This precludes strategies adopted for isoreticular metal-organic frameworks, where addition of a small group, such as a methyl group, does not affect the basic framework topology. Here, we narrow the pore size of a cage molecule, CC3, in a systematic way by introducing methyl groups into the cage windows. Computational crystal structure prediction was used to anticipate the packing preferences of two homochiral methylated cages, CC14-R and CC15-R, and to assess the structure-energy landscape of a CC15-R/CC3-S cocrystal, designed such that both component cages could be directed to pack with a 3-D, interconnected pore structure. The experimental gas sorption properties of these three cage systems agree well with physical properties predicted by computational energy-structure-function maps.

SIGUEME: Technology-based intervention for low-functioning autism to train skills to work with visual signifiers and concepts.

BACKGROUND: People with low-functioning ASD and other disabilities often find it difficult to understand the symbols traditionally used in educational materials during the learning process. Technology-based interventions are becoming increasingly common, helping children with cognitive disabilities to perform academic tasks and improve their abilities and knowledge. Such children often find it difficult to perform certain tasks contained in educational materials since they lack necessary skills such as abstract reasoning. In order to help these children, the authors designed and created SIGUEME to train attention and the perceptual and visual cognitive skills required to work with and understand graphic materials and objects. METHODS: A pre-test/post-test design was implemented to test SIGUEME. Seventy-four children with low-functioning ASD (age=13.47, SD=8.74) were trained with SIGUEME over twenty-five sessions and compared with twenty-eight children (age=12.61, SD=2.85) who had not received any intervention. RESULTS: There was a statistically significant improvement in the experimental group in Attention (W=-5.497, p<0.001). There was also a significant change in Association and Categorization (W=2.721, p=0.007) and Interaction (W=-3.287, p=0.001). CONCLUSIONS: SIGUEME is an effective tool for improving attention, categorization and interaction in low-functioning children with ASD. It is also a useful and powerful instrument for teachers, parents and educators by increasing the child's motivation and autonomy.

Functional materials discovery using energy-structure-function maps.

Molecular crystals cannot be designed in the same manner as macroscopic objects, because they do not assemble according to simple, intuitive rules. Their structures result from the balance of many weak interactions, rather than from the strong and predictable bonding patterns found in metal-organic frameworks and covalent organic frameworks. Hence, design strategies that assume a topology or other structural blueprint will often fail. Here we combine computational crystal structure prediction and property prediction to build energy-structure-function maps that describe the possible structures and properties that are available to a candidate molecule. Using these maps, we identify a highly porous solid, which has the lowest density reported for a molecular crystal so far. Both the structure of the crystal and its physical properties, such as methane storage capacity and guest-molecule selectivity, are predicted using the molecular structure as the only input. More generally, energy-structure-function maps could be used to guide the experimental discovery of materials with any target function that can be calculated from predicted crystal structures, such as electronic structure or mechanical properties.

Ketonic decarboxylation reaction mechanism: a combined experimental and DFT study.

The ketonic decarboxylation of carboxylic acids has been carried out experimentally and studied theoretically by DFT calculations. In the experiments, monoclinic zirconia was identified as a good catalyst, giving high activity and high selectivity when compared with other potential catalysts, such as silica, alumina, or ceria. It was also shown that it could be used for a wide range of substrates, namely, for carboxylic acids with two to eighteen carbon atoms. The reaction mechanism for the ketonic decarboxylation of acetic acid over monoclinic zirconia was investigated by using a periodic DFT slab model. A reaction pathway with the formation of a ß-keto acid intermediate was considered, as well as a concerted mechanism, involving simultaneous carbon-carbon bond formation and carbon dioxide elimination. DFT results showed that the mechanism with the ß-keto acid was the kinetically favored one and this was further supported by an experiment employing a mixture of isomeric (linear and branched) pentanoic acids.

Experimental and theoretical determination of adsorption heats of CO(2) over alkali metal exchanged ferrierites with different Si/Al ratio.

The adsorption of CO(2) in Li-, Na-, and K-FER was investigated by a combination of volumetric adsorption experiments, FTIR spectroscopy, and density functional theory. Experimental isosteric heats of CO(2), Q(st), depend significantly on the cation size, cation concentration, and on the amount of adsorbed CO(2). The differences observed in experimentally determined isosteric heats were interpreted at the molecular level based on good agreement between experimental and calculated characteristics. The highest interaction energies were found for CO(2) adsorbed on so-called "dual cation sites" in which CO(2) is bridged between two alkali metal cations. The formation of CO(2) adsorption complexes on dual cation sites is particularly important on Na-FER and K-FER samples with higher cation concentration. On the contrary, the differences in Q(st) observed for Li-FER samples are due to the changes in the Li(+) coordination with the framework. The DFT/CC calculations show that the dispersion interactions between CO(2) and the zeolites framework are rather large (about -20 kJ mol(-1)).

Computational and variable-temperature infrared spectroscopic studies on carbon monoxide adsorption on zeolite Ca-A.

Carbon monoxide adsorption on LTA (Linde type 5A) zeolite Ca-A is studied by using a combination of variable-temperature infrared spectroscopy and computational methods involving periodic density functional calculations and the correlation between stretching frequency and bond length of adsorbed CO species (nu(CO)/r(CO) correlation). Based on the agreement between calculated and experimental results, the main adsorption species can be identified as bridged Ca(2+)...CO...Ca(2+) complexes formed on dual-cation sites constituted by a pair of nearby Ca(2+) cations. Two types of such species can be formed: One of them has the two Ca(2+) ions located on six-membered rings of the zeolite framework and is characterized by a C-O stretching frequency in the range of 2174-2179 cm(-1) and an adsorption enthalpy of -31 to -33 kJ mol(-1), whereas the other bridged CO species is formed between a Ca(2+) ion located on an eight-membered ring and another one on a nearby six-membered ring and is characterized by nu(CO) in the range 2183-2188 cm(-1) and an adsorption enthalpy of -46 to -50 kJ mol(-1). Ca(2+)...CO monocarbonyl complexes are also identified, and at a relatively high CO equilibrium pressure, dicarbonyl species can also be formed.

Theoretical investigation of dinitrosyl complexes in Cu-zeolites as intermediates in deNOx process.

The structure and stability of nitrosyl complexes formed in Cu-FER zeolite were investigated using a periodic DFT model. The reliability of both DFT methods and cluster models when describing the Cu(+) interaction with NO molecules was examined. The relative stabilities of mononitrosyl complexes on various Cu(+) sites in Cu-FER are governed by the deformation energy of the particular site. Three types of dinitrosyl complexes with different coordination on the Cu(+) cation were identified: (i) four-fold tetrahedral, (ii) four-fold square-planar and (iii) three-fold trigonal-planar complexes. The most stable dinitrosyl complex, formed when the two NO molecules interact with Cu(+)via the N atom, has a tetrahedral coordination on Cu(+). The cyclic adsorption complex, having a square-planar arrangement of ligands on Cu(+) and interaction via O atoms, is only about 10 kJ mol(-1) less stable than the N-down dinitrosyl complex. This cyclic dinitrosyl complex is suggested to be the key intermediate in the deNO(x) process taking place in Cu-zeolites.

Computational study of location and role of fluoride in zeolite structures.

The distribution of fluoride ions has been studied in the pure silica IFR, ITH, IWR, STF and STT zeolite structures using computational techniques. The interactions between the F- and SDA+ ions (where SDA is the organic structure directing agent) are able to explain the F- cage occupation found experimentally. While studying the short-range fluoride-framework interactions, a relationship was found between the Si atoms forming the pentacoordinated units and the lowest F- defect energies, which rationalizes the experimental Si-F bonding in terms of energetic stability. It is proposed that the F- location is governed by a two step process. In a first stage, the electrostatic long-range forces and, especially, the interactions between the F- and the SDA+ ions, decide which cage will be filled with F-; in a second stage, once the F- cage location is decided, the F- forms a covalent bond with a Si site to form an energetically stable pentacoordinated unit [SiO4/2F]-.

Computational study of 19F NMR spectra of double four ring-containing Si/Ge-zeolites.

(19)F NMR chemical shifts are calculated in order to study the F(-) environment in double four ring (D4R) containing Si/Ge-zeolites. The calculations with the DFT/CSGT/B3PW91 methodology yielded an agreement within 2 ppm with respect to the experimental peaks corresponding to the D4R units containing 8Si0Ge, 7Si1Ge and 0Si8Ge of the octadecasil zeolite. The optimisation of the 7Si1Ge-, 6Si2Ge-, 5Si3Ge- and 4Si4Ge-D4R units with DFT/B3LYP methodology shows that a covalent Ge-F bond is formed and therefore a Ge atom in the D4R is pentacoordinated. The displacement of the fluoride ion towards a Ge atom in the Ge-containing D4R units locates four Si/Ge atoms in the close vicinity of the F(-) and this makes possible a rationalization of the (19)F NMR signals in groups according to the number of Si (n) and Ge (m) atoms in the nearest F(-) environment, F-Si(n)Ge(m) (where n+m=4). Thus, the calculated chemical shifts show that higher values are observed when the number of Ge atoms in the nearest F(-) environment increases.

Pentacoordinated germanium in AST zeolite synthesised in fluoride media. A 19F NMR validated computational study.

A computational study shows that Ge is pentacoordinated in the double four rings (D4R) of Si/Ge AST zeolites; the calculated chemical shifts of F-D4R containing 8Si, 7Si1Ge and 8Ge reproduce the trends of 19F NMR experiments.

Evaluación de cuatro métodos rápidos para la investigación de la capacidad toxigénica de las cepas de clostridium difficile aisladas en un medio selectivo / Evaluation of four rapid methods for the investigation of the toxigenic capacity of Clostridium difficile strains isolated in a selective medium

Fundamento: El diagnóstico por cultivo de la enfermedad asociada a Clostridium difficile requiere confirmar la capacidad toxigénica de los aislamientos. La técnica de referencia es la detección de la citotoxina por cultivo celular tras el crecimiento del microorganismo durante 3-5 días en medio líquido, implicando una demora en el diagnóstico final. En este estudio, se comparan de forma retrospectiva 4 métodos rápidos para la investigación de la toxigenicidad in vitro de las cepas de C. difficile. Métodos: Se han utilizado 106 aislamientos clínicos de C. difficile (72 toxigénicos y 34 no toxigénicos), y 16 de otras especies de Clostridium. Los cuatro métodos se llevaron a cabo directamente a partir de las colonias aisladas en medio sólido. Los métodos evaluados fueron: a) detección directa de la citotoxina; b) dos técnicas de amplificación por reacción en cadena de la polimerasa (PCR) de los genes codificantes de toxina A y B, respectivamente, y c) detección de la toxina A por enzimoinmunoanálisis (VIDAS CDA2). En todos ellos, el tiempo total de procesamiento fue inferior al de una jornada laboral. Resultados: Sólo las 72 cepas de C. difficile toxigénicas mostraron resultados positivos por cultivo celular y por las técnicas de PCR (sensibilidad y especificidad del 100 por ciento). En cuanto a la técnica de VIDAS, hubo 14 resultados falsos negativos entre las 49 cepas de C. difficile toxigénicas investigadas, aunque todas estas cepas fueron positivas en pruebas repetidas. Conclusiones: Aunque todos los métodos fueron eficaces, la detección de citotoxina directa de colonias es una técnica sencilla, rápida y adecuada para aquellos laboratorios que dispongan de cultivos celulares (AU)