Giant molecules or tiny crystals?

Nature Materials has a News and Views article by Ian Robinson titled “Coherent diffraction: Giant molecules or tiny crystals?”, which reviews recent coherent electron diffraction results by Huang et al. featured here earlier. One of the interesting points made in this mini-review is the phase diagram on the left showing a transition from bulk cubic crystal to decahedral and icosahedral structures, including quasi-molten and liquid phases.

Keyhole Imaging, Relaxation in Nanoparticles, CDW correlations

In advanced publication of Nature Physics, Brian Abbey and colleagues present a new technique, called “Keyhole Coherent Diffractive Imaging”, which enables them to study extended objects (in similar fashion as ptychography, but based on a somewhat different geometry). The basic idea of KCDI is to combine Fresnel and Fraunhoffer imaging in a divergent (curved) wavefront by placing an imaged object behind the focal spot of a lens and use this additional information to reconstruct the wavefront. It is somewhat counter-intuitive to understand why curved wavefronts should provide a faster phase-retrieval algorithm convergence than flat wavefronts, but it’s a bit like mixing near-field and far-field techniques.

In advanced publication of Nature Materials, Urbana group lead by Jim Zuo show how application of coherent electron diffraction imaging (very similar to x-ray techniques) can reveal the relationship between the coordination number of Au atoms within a ~4 nm nanoparticle and the out-of-plane bond length. Electrons interact much stronger with matter than x-rays and one could argue that electrons are better for imaging of small nanosized objects, while x-rays are better for imaging extended micron-sized objects. Surface relaxation is a well-known phenomenon in surface science – due to reduced number of near-neighbors, atoms in the near-surface region end up with “dangling bonds” effect – and by turning these bonds inward the atoms can reduce out-of-plane atomic distance. Zuo and his group provide a very detailed analysis of surface relaxation for various facets of Au nanoparticles, as a function of near-neighbor coordination number.

And in a recent issue of Physical Review Letters, David LeBolloch’ and colleagues show that charge density wave condensate in blue bronze compound can spontaneously develop long-range correlations (up to micron-size) when the charge density waves is depinned due to applied current and is in a sliding state (imagine a particle on a washboard potential which is getting tilted).

Xraying Nanoparticles in Ball-Lightning and Fuel Injection jets

Observations of ball-lightning – long-lived (2 to 50 seconds) bright fireballs size of baseball to beach ball – have been observed for centuries. Previous theoretical work ascribes the longevity of the ball lightnings to the slow oxidation process of silicon, forming nanoparticle networks. Now, Mitchell et al. Phys. Rev. Lett. 100, 065001 (2008) have created artificial ball-lightning using localized microwaves and have studied them in-situ with synchrotron radiation (using small-angle x-ray scattering), proving that the fireballs do indeed contain nanoparticles with sizes of the order 50 nm.

Small Angle X-ray Scattering, or SAXS, has been used to all kinds of samples – liquid, vapor or solid, but this may be the first time this technique was applied to plasma.

Meanwhile, Wang et al. (Nature Physics, advanced publication) performed an ultra-fast time resolved study of morphology of optically dense jets from fuel injector nozzle. The achieved microsecond temportal resolution is due to application of time-resolved full-field phase contrast imaging. Unlike typical radiography (such as used at the dentist’s office) that is sensitive to the mass density (adsorption) of material through intensity measurements, phase contrast measurements rely on phase changes.

For more details on phase contrast imaging see Wilkins et al., Nature 384, 335 – 338 (28 November 1996)

Techniques using visible light scattering are suffering from problems due to multiple scattering from various interfaces of jet droplets – ironically, these interfaces are precisely what serves as a contrast mechanism in the x-ray phase contrast imaging technique used by Wang et. al in this study.

Nanoparticle Self-assembly with DNA

Image on the left is the cover of Jan. 31 issue of Nature.

Anyone who took high school chemistry has played with “sticks and balls” models of molecules or crystalline atoms. There are magnetic toy sets which allow kids to assemble their own version of crystals.

A similar feat, but on nanoscale, was accomplished by two groups – one at Brookhaven (Nykypanchuk et. al  Nature 451, 549-552 (2008)) and another at Northwestern (Park et. al, Nature 451, 553-556 (2008)).

The basic idea behind these two experiments is to graft different strands of DNA molecules onto particles, creating two “species” of particles with complimentary pairs of DNA strands. These two different types of strands can merge together into a double helix at high temperatures, making a strong connection between particles of the opposite species. The result is a cubic structure, similar to ion salts.

The nanoparticle crystals held together by DNA molecules are rather fragile, and most of volume is occupied by water. The typical size of the unit cell is on the order of 35-50 nm, with particle size just 10 nm in size. The nanoparticles therefore occupy only a tiny fraction of the total crystal volume, with density of such “fluffy” crystals less than milk foam in your latte.