Closed-surface hexameric metal-organic nanocapsules derived from cavitand ligands

Assembly of cavitand ligands, (4-), and Zn2+ ions yields a one-dimensional polymer comprised of hexameric, closed-surface, metal-organic nanocapsules.     

Quantitative studies of long-term stable, top-down fabricated silicon nanowire pH sensors

We report a simple and effective method to develop long-term stable, top-down fabricated silicon nanowire (SiNW) pH sensors along with systematic studies on the performance of the sensors. In this work, we fabricated the SiNW pH sensors based on top-down fabrication processes. In order to improve the stability of the sensor performance, the sensors were coated with a passivation layer (PECVD-based silicon nitride) for effective electrical insulation and ion-blocking. The stability, pH sensitivity, and repeatability of the sensor response are critically analyzed with regard to the physics of sensing interface between sample liquid and the sensor surface. Also, trade-off between the stability and pH sensitivity of the sensor response is discussed.     

Structures of gas-phase C2F 7 + ions

In an ion cyclotron resonance spectrometer, less than 96% of the C₇F ₇ ⁺ cation formed on electron ionization of perfluorotoluene reacts with hexamethyldisilazane. In contrast, the C₇F ₇ ⁺ from perfluoronorbornadiene or perfluorobicyclo[3.2.O]hepta-2,6-diene is nonreactive with hexamethyldisilazane. Collision-induced dissociation results support this dichotomy, although the evidence is not as clear-cut. The reactive ion is assigned the benzyl structure and the nonreactive ion the tropyl structure, on the basis of analogy with the protio cases. By AM1 calculations, the perfluorobenzyl ion is 25 kcal/mol more stable than the perfluorotropyl ion, the opposite of the situation for the protio analogs (? 12 kcal/mol). Ab initio calculations at the 3–21G level agree with the semiempirical energy difference to within 0.4 kcal/mol; at the more appropriate 6–31G*/MP2 level, the perfluorobenzyl cation is 9.7 kcal/mol more stable than the perfluorotropyl cation.     

The generality of architectural isomerism in designer inclusion frameworks.

We describe herein new structural isomers of a lamellar host system based on organodisulfonate "pillars" that connect opposing hydrogen-bonded sheets, consisting of topologically complementary guanidinium (G) ions and sulfonate (S) groups, to generate inclusion cavities between the sheets. These new isomers-zigzag brick, double brick, V-brick, and crisscross bilayer-expand significantly on our earlier report of architectural isomerism displayed by the discrete bilayer and simple brick forms. We demonstrate here that the discrete bilayer-simple brick isomerism, which was limited to several host-guest combinations based on the G(2)(4,4'-biphenyldisulfonate) host and one pair of compounds based on the G(2)(2,6-naphthalenedisulfonate), can be generalized to other organodisulfonate pillars. Furthermore, in many cases the selectivity toward the different framework isomers reflects a rather systematic templating role of the guest molecules and host-guest recognition during assembly of the lattice. We also describe a convenient approach to identifying and classifying the innumerable possible host architectures based upon the pillar projection topologies for the GS sheets and the intersheet connectivities. The discovery of these new architectures reveals a structural versatility for this class of materials that exceeds initial expectations and observations. Each topology produces different connectivities between the sheets in the third dimension that endows each framework isomer with uniquely shaped and sized inclusion cavities, enabling this host system to conform readily to different guests. The unlimited number of architectures available, combined with the inherent conformational softness and structural tunability of these host lattices, suggests a near universality for the GS system with respect to guest inclusion.     

A single-molecule probe based on intramolecular electron transfer

Detecting structure, dynamics, and chemical reactions at the single-molecule level represents the ultimate degree of sensitivity for sensing and imaging. There is a tremendous need to develop new molecular systems and methodology for single-molecule-based sensing. This work presents for the first time the single-molecule spectroscopy of a new molecular probe which uses an intramolecular electron transfer mechanism to detect binding, local structure, and interfacial processes. Moreover, we show how information about the interaction of these probes with their environment is obtained from an analysis of the intensity, duration and time-varying behavior of the single-molecule fluorescence.