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Compared with batch and vapor diffusion methods, counter diffusion can generate larger and higher-quality protein crystals yielding improved diffraction data and higher-resolution structures. Typically, counter-diffusion experiments are conducted in elongated chambers, such as glass capillaries, and the crystals are either directly measured in the capillary or extracted and mounted at the X-ray beamline. Despite the advantages of counter-diffusion protein crystallization, there are few fixed-target devices that utilize counter diffusion for crystallization. In this article, different designs of user-friendly counter-diffusion chambers are presented which can be used to grow large protein crystals in a 2D polymer microfluidic fixed-target chip. Methods for rapid chip fabrication using commercially available thin-film materials such as Mylar, propylene and Kapton are also detailed. Rules of thumb are provided to tune the nucleation and crystal growth to meet users' needs while minimizing sample consumption. These designs provide a reliable approach to forming large crystals and maintaining their hydration for weeks and even months. This allows ample time to grow, select and preserve the best crystal batches before X-ray beam time. Importantly, the fixed-target microfluidic chip has a low background scatter and can be directly used at beamlines without any crystal handling, enabling crystal quality to be preserved. The approach is demonstrated with serial diffraction of photoactive yellow protein, yielding 1.32 Å resolution at room temperature. Fabrication of this standard microfluidic chip with commercially available thin films greatly simplifies fabrication and provides enhanced stability under vacuum. These advances will further broaden microfluidic fixed-target utilization by crystallographers.
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Disequilibrium crystallization and rapid crystal growth: a case study of orbicular granitoids of magmatic origin
Archaean orbicular granitoids from western Australia were investigated to better understand crystal growth processes. The orbicules are dioritic to tonalitic spheroids dispersed in a granitic host magma. Most orbicules have at least two to three concentric bands composed of elongate and radially oriented hornblendes with interstitial plagioclase. Each band consists of a hornblende-rich outer layer and a plagioclase-rich inner layer. Doublet band thicknesses increase, crystal number density decreases, and grain size increases from rim to core, suggesting crystallization was more rapid on the rims than in the core. Despite these radial differences, mineral mode and bulk composition of each band are similar, indicating limited crystal-melt segregation during crystallization. These observations lead us to suggest that the orbicules represent slowly quenched blobs of hot dioritic to tonalitic liquids injected into a cooler granitic magma. The oscillatory bands in the orbicules can be explained by rapid, disequilibrium crystallization (supercooling). In particular, a linear correlation between bandwidth and radial distance from orbicule rim can be explained by transport-limited crystallization, wherein crystallization timescales are shorter than chemical diffusion timescales. The slope of this linear relationship corresponds to the square root of the ratio between effective chemical diffusivity in the growth medium and thermal diffusivity, resulting in effective chemical diffusivities of 3 × 10−8 m2/s. These high effective diffusivities require static diffusion through a free volatile phase (fluid) and/or a strong advective/convective component in the fluid. Regardless of the mechanisms, these effective diffusivities can be used to estimate growth rates of ~10−6 m/s or 0.4 cm/hr. Our results indicate that crystals can grow rapidly, possibly facilitated by fluids and dynamic conditions. These rapid growth rates suggest that centimetre or larger crystals, such as in porphyritic and pegmatitic systems, can conceivably grow within days.
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- Award ID(s):
- 1753599
- PAR ID:
- 10198867
- Date Published:
- Journal Name:
- International Geology Review
- ISSN:
- 0020-6814
- Page Range / eLocation ID:
- 1 to 17
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1080/00206814.2020.1734975
