Measurement of dilute 29Si species in solution using a large volume coil and DEFT NMR

A large-sample-volume nuclear magnetic resonance (NMR) spectroscopy probehead has been developed for the detection and characterization of low concentrations of 29Si species in aqueous solution. The approach described entails the use of a large-diameter radio frequency solenoid coil that permits substantially larger sample volumes to be investigated at moderate magnetic field strengths, compared with conventional NMR probehead configurations. In addition, difficulties presented by long 29Si T1 relaxation times have been circumvented by using the DEFT NMR pulse sequence, which permits more rapid signal averaging. Through a combination of these hardware and methodological improvements, high-resolution 29Si NMR spectra have been obtained at 4.2 T (29Si resonance frequency = 36.8 MHz) for an 800 microM solution of 96% 29Si-enriched silicic acid, H4SiO4 (pH approximately 8), with a signal-to-noise ratio of 16 and a line width of 31 Hz after 3 h of total measurement time.

Mirrorless lasing from mesostructured waveguides patterned by soft lithography

Mesostructured silica waveguide arrays were fabricated with a combination of acidic sol-gel block copolymer templating chemistry and soft lithography. Waveguiding was enabled by the use of a low-refractive index (1.15) mesoporous silica thin film support. When the mesostructure was doped with the laser dye rhodamine 6G, amplified spontaneous emission was observed with a low pumping threshold of 10 kilowatts per square centimeter, attributed to the mesostructure's ability to prevent aggregation of the dye molecules even at relatively high loadings within the organized high-surface area mesochannels of the waveguides. These highly processible, self-assembling mesostructured host media and claddings may have potential for the fabrication of integrated optical circuits.

Hierarchically ordered oxides

Porous silica, niobia, and titania with three-dimensional structures patterned over multiple length scales were prepared by combining micromolding, polystyrene sphere templating, and cooperative assembly of inorganic sol-gel species with amphiphilic triblock copolymers. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from 10 nanometers to several micrometers. The respective ordered structures can be independently modified by choosing different mold patterns, latex spheres, and block copolymers. The examples presented demonstrate the compositional and structural diversities that are possible with this simple approach.

Direct determination of motional correlation times by 1D MAS and 2D exchange NMR techniques

One- and two-dimensional static and magic-angle spinning (MAS) exchange NMR experiments for quantifying slow (tauc > 1 ms) molecular reorientation dynamics are analyzed, emphasizing the extent to which motional correlation times can be extracted directly from the experimental data. The static two-dimensional (2D) exchange NMR experiment provides geometric information, as well as exchange time scales via straightforward and model-free application of Legendre-type orientational autocorrelation functions, particularly for axially symmetric interaction tensors, as often encountered in solid-state 2H and 13C NMR. Under conditions of MAS, increased sensitivity yields higher signal-to-noise spectra, with concomitant improvement in the precision and speed of correlation time measurements, although at the expense of reduced angular (geometric) resolution. For random jump motions, one-dimensional (1D) exchange-induced sidebands (EIS) 13C NMR and the recently developed ODESSA and time-reverse ODESSA experiments complement the static and MAS two-dimensional exchange NMR experiments by providing faster means of obtaining motional correlation times. For each of these experiments, the correlation time of a dynamic process may be obtained from a simple exponential fit to the integrated peak intensities measured as a function of mixing time. This is demonstrated on polycrystalline dimethylsulfone, where the reorientation rates from EIS, ODESSA, time-reverse ODESSA, and 2D exchange are shown to be equivalent and consistent with literature values. In the analysis, the advantages and limitations of the different methods are compared and discussed. Copyright 1998 Academic Press.

Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores

Use of amphiphilic triblock copolymers to direct the organization of polymerizing silica species has resulted in the preparation of well-ordered hexagonal mesoporous silica structures (SBA-15) with uniform pore sizes up to approximately 300 angstroms. The SBA-15 materials are synthesized in acidic media to produce highly ordered, two-dimensional hexagonal (space group p6mm) silica-block copolymer mesophases. Calcination at 500 degrees C gives porous structures with unusually large interlattice d spacings of 74.5 to 320 angstroms between the (100) planes, pore sizes from 46 to 300 angstroms, pore volume fractions up to 0.85, and silica wall thicknesses of 31 to 64 angstroms. SBA-15 can be readily prepared over a wide range of uniform pore sizes and pore wall thicknesses at low temperature (35 degrees to 80 degrees C), using a variety of poly(alkylene oxide) triblock copolymers and by the addition of cosolvent organic molecules. The block copolymer species can be recovered for reuse by solvent extraction with ethanol or removed by heating at 140 degrees C for 3 hours, in both cases, yielding a product that is thermally stable in boiling water.