The x-ray diffracting properties of several types of layered synthetic microstructures (LSMs) and their use in the measurement of elements traditionally covered by the acid phthalate and Langmuir-Blodgett diffracting structures have been extended in this application to cover oxygen, nitrogen, carbon, and boron. A major problem in working in the longer wavelength region is that large incremental differences in wavelength per atomic number step make it difficult to obtain well-balanced combinations of wavelength range and angular dispersion with the limited set of "natural" diffracting structures (crystals) available. In contrast, it is possible to produce LSM structures with more desirable diffraction and dispersion properties over most of the long wavelength characteristic x-ray emission region. By developing structures that suppress higher order spectra and by clever selection of substrate composition, we have been able to extend both performance and range of application beyond initial expectations. This paper describes some of the work that has been done to provide such optimization and then discusses results obtained in the application of these diffracting structures for spectrochemical analysis.