Understanding and controlling the nucleation and growth of metal-organic frameworks.

Metal-organic frameworks offer a diverse landscape of building blocks to design high performance materials for implications in almost every major industry. With this diversity stems complex crystallization mechanisms with various pathways and intermediates. Crystallization studies have been key to the advancement of countless biological and synthetic systems, with MOFs being no exception. This review provides an overview of the current theories and fundamental chemistry used to decipher MOF crystallization. We then discuss how intrinsic and extrinsic synthetic parameters can be used as tools to modulate the crystallization pathway to produce MOF crystals with finely tuned physical and chemical properties. Experimental and computational methods are provided to guide the probing of MOF crystal formation on the molecular and bulk scale. Lastly, we summarize the recent major advances in the field and our outlook on the exciting future of MOF crystallization.

Role of Molecular Modification and Protein Folding in the Nucleation and Growth of Protein-Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) are a class of porous nanomaterials that have been extensively studied as enzyme immobilization substrates. During in situ immobilization, MOF nucleation is driven by biomolecules with low isoelectric points. Investigation of how biomolecules control MOF self-assembly mechanisms on the molecular level is key to designing nanomaterials with desired physical and chemical properties. Here, we demonstrate how molecular modifications of bovine serum albumin (BSA) with fluorescein isothiocyanate (FITC) can affect MOF crystal size, morphology, and encapsulation efficiency. Final crystal properties are characterized using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), fluorescent microscopy, and fluorescence spectroscopy. To probe MOF self-assembly, in situ experiments were performed using cryogenic transmission electron microscopy (cryo-TEM) and X-ray diffraction (XRD). Biophysical characterization of BSA and FITC-BSA was performed using ζ potential, mass spectrometry, circular dichroism studies, fluorescence spectroscopy, and Fourier transform infrared (FTIR) spectroscopy. The combined data reveal that protein folding and stability within amorphous precursors are contributing factors in the rate, extent, and mechanism of crystallization. Thus, our results suggest molecular modifications as promising methods for fine-tuning protein@MOFs' nucleation and growth.

Demonstrating correction of low levels of astigmatism with realistic scenes.

PURPOSE AND METHOD: Modern standard visual acuity tests are primarily designed as diagnostic tools for use during subjective refraction and normally bear little relation to real-world situations. We have developed a methodology to create realistic rendered scenes that demonstrate potential vision improvement in a relevant and engaging way. Low-cylindrical refractive error can be made more noticeable by optimizing the contrast and spatial frequencies, and by testing four different visual perception skills: motion tracking, pattern recognition, visual clutter differentiation and contrast sensitivity. Using a 1.00DC lens during iteration, we created a range of still and video scenes before optimizing to a selection 3-D rendered street scenes. These were assessed on everyday relevance, emotional and visual engagement and sensitivity to refractive correction for low-cylinder astigmats (0.75-1.00DC, n=74) wearing best spherical equivalent correction and then with astigmatism corrected. RESULTS AND CONCLUSIONS: The most promising visual elements involved or combined optimized textures, distracting patterns behind text, faces at a distance, and oblique text. 91.9% of subjects (95% CI: 83.2, 97.0) reported an overall visual improvement when viewing the images with astigmatic correction, and 96% found the images helpful to determine which type of contact lens to use. Our method, which combines visual science with design thinking, takes a new approach to creating vision tests. The resultant test scenes can be used to improve patient interaction and help low cylinder astigmats see relevant, every-day benefits in correcting low levels (0.75 & 1.00DC) of astigmatism.