Amorphous zeolitic imidazolate frameworks (ZIFs) offer promising applications as novel functional materials. Herein, amorphization of ZIF-L through scanning-electron-beam exposure is demonstrated, based on amorphization of individual ZIF-L crystals. The amorphized ZIF product has drastically increased stability against dissolution in water. An electron dose that allows for complete preservation of amorphous particles after immersion in water is established, resulting in new shapes of amorphous ZIF-L with spatial control at the sub-micrometer length scale. Changed water stability as a consequence of scanning-electron-beam exposure is demonstrated for three additional metal-organic frameworks (ZIF-8, Zn(BeIm)OAc, MIL-101), highlighting the potential use of an electron beam for top-down MOF patterning. Lastly, recrystallization of ZIF-L in the presence of linker is studied and shows distinct differences for crystalline and amorphized material.

The feasibility of monitoring the permeation of chain perdeuterated 1,2-dipalmitoylphosphatidylcholine (DPPC-d62) and 1-palmitoyl-d31, 2-oleoylphosphatidylcholine (P-d31OPC) vesicles into pigskin using infrared (IR) microscopic imaging and confocal Raman microscopy was demonstrated. The former technique permits the examination of the relative concentration of molecular species (e.g., endogenous and exogenous lipids and proteins) over spatial areas, approximately 1 mm, with a spatial resolution of approximately 10-12 microm. In contrast, Raman microscopy allows the confocal examination of tissue at depths up to 100 microm with a pixel size of about 2-3 microm3. Spectral signal/noise, however, is reduced from IR and significantly smaller areas are generally monitored. The permeation of the gel phase DPPC-d62 was limited to approximately 5-15 microm, whereas the liquid-crystalline phase P-d31OPC permeated to substantially greater depths (35-100 microm), at times ranging up to 24 h after application. The results are generally in accord with literature values. In addition, the state of the P-d31OPC (intact vesicles or molecularly dispersed with skin constituents) was evaluated from the spatial dependence of the deuteriopalmitate chain conformational order. Upon permeation, the chains became more ordered. The advantages and limitations of these imaging technologies are discussed.

Confocal Raman microscopy data are reported for a laminated polymer (Paramount) and for pigskin. The nature of the laminated structure of the polymer provides a useful test for evaluation of thickness distortions in confocal measurements in soft samples, which are found to be quite significant. The spatial variation in line profiles generated from univariate analyses with scores derived from factor loadings are consistent for both samples and provide distinct diagnostic markers for stratum corneum and epidermis regions of skin. Univariate analysis of the C-C stretching region of skin reveals a spatial dependence of chain conformational order. In addition, variations in keratin-containing areas of the stratum corneum are readily identified from area maps of the S-S stretching vibrations. These data indicate that confocal Raman imaging studies of molecular structure changes in particular regions of skin during pathological processes will prove quite valuable in dermatology.

The development of methods that allow microscale studies of complex biomaterials based on their molecular composition is of great interest to a wide range of research fields. We show that stimulated Raman scattering (SRS) microscopy is an excellent analytical tool to study distributions of different biomolecules in multiphasic systems. SRS combines the label-free molecular specificity of vibrational spectroscopy with an enhanced sensitivity due to coherent excitation of molecular vibrations. Compared to previous imaging studies using coherent anti-Stokes Raman scattering microscopy, the main advantage of SRS microscopy is the absence of the unwanted nonresonant background, which translates into a superior sensitivity and undistorted vibrational spectra. We compare spectra of complex materials obtained with stimulated Raman scattering and spontaneous Raman scattering in the crowded fingerprint region. We find that, as expected, there is excellent correspondence and that the SRS spectra are free from interference from background fluorescence. In addition, we show high-resolution imaging of the distributions of selected biomolecules, such as lipids and proteins, in food products with SRS microscopy.