Chemically tailoring nanopores for single-molecule sensing and glycomics.

A nanopore can be fairly-but uncharitably-described as simply a nanofluidic channel through a thin membrane. Even this simple structural description holds utility and underpins a range of applications. Yet significant excitement for nanopore science is more readily ignited by the role of nanopores as enabling tools for biomedical science. Nanopore techniques offer single-molecule sensing without the need for chemical labelling, since in most nanopore implementations, matter is its own label through its size, charge, and chemical functionality. Nanopores have achieved considerable prominence for single-molecule DNA sequencing. The predominance of this application, though, can overshadow their established use for nanoparticle characterization and burgeoning use for protein analysis, among other application areas. Analyte scope continues to be expanded, and with increasing analyte complexity, success will increasingly hinge on control over nanopore surface chemistry to tune the nanopore, itself, and to moderate analyte transport. Carbohydrates are emerging as the latest high-profile target of nanopore science. Their tremendous chemical and structural complexity means that they challenge conventional chemical analysis methods and thus present a compelling target for unique nanopore characterization capabilities. Furthermore, they offer molecular diversity for probing nanopore operation and sensing mechanisms. This article thus focuses on two roles of chemistry in nanopore science: its use to provide exquisite control over nanopore performance, and how analyte properties can place stringent demands on nanopore chemistry. Expanding the horizons of nanopore science requires increasing consideration of the role of chemistry and increasing sophistication in the realm of chemical control over this nanoscale milieu.

Sedimentary laminations in the Isheyevo (CH/CBb) carbonaceous chondrite formed by gentle impact-plume sweep-up.

Prominent macroscopic sedimentary laminations, consisting of mm- to cm-thick alternating well-sorted but poorly mixed silicate and metal-rich layers cut by faults and downward penetrating load structures, are prevalent in the Isheyevo (CH/CBb) carbonaceous chondrite. The load structures give the up direction of this sedimentary rock that accumulated from in-falling metal- and silicate-rich grains under near vacuum conditions onto the surface of an accreting planetesimal. The Isheyevo meteorite is the end result of a combination of events and processes that we suggest was initiated by the glancing blow impact of two planetesimals. The smaller impactor was disrupted forming an impact plume downrange of the impact. The components within the plume were aerodynamically size sorted by the nebular gas and swept up by the impacted planetesimal before turbulent mixing within the plume could blur the effects of the sorting. This plume would have contained a range of materials including elementally zoned Fe-Ni metal grains that condensed in the plume to disrupted unaltered material from the crust of the impactor, such as the hydrated matrix lumps. The juxtaposition of hydrated matrix lumps, some of which have not been heated above 150 °C, together with components that formed above 1000 °C, is compelling evidence that they were swept up together. Sweep-up would have occurred as the rotating impactor moved through the plume producing layers of material: the Isheyevo sample thus represents material accumulated while that part of the rotating planetesimal moved into the plume. Vibrations from subsequent impacts helped to form the load structures and induced weak grading within the layers via kinetic sieving. Following sweep-up, the particles were compacted under low static temperatures as evidenced by the preservation of elementally zoned Fe-Ni metal grains with preserved martensite α 2 cores, distinct metal-metal grain boundaries, and metal-deformation microstructures. This meteorite provides evidence of gentle layer-by-layer accretion in the early Solar System, and also extends the terrestrial sedimentary source-to-sink paradigm to a near vacuum environment where neither fluvial nor aeolian processes operate.

NEW INSIGHT INTO THE SOLAR SYSTEM'S TRANSITION DISK PHASE PROVIDED BY THE METAL-RICH CARBONACEOUS CHONDRITE ISHEYEVO.

Many aspects of planet formation are controlled by the amount of gas remaining in the natal protoplanetary disks (PPDs). Infrared observations show that PPDs undergo a transition stage at several megayears, during which gas densities are reduced. Our Solar System would have experienced such a stage. However, there is currently no data that provides insight into this crucial time in our PPD's evolution. We show that the Isheyevo meteorite contains the first definitive evidence for a transition disk stage in our Solar System. Isheyevo belongs to a class of metal-rich meteorites whose components have been dated at almost 5 Myr after formation of Ca, Al-rich inclusions, and exhibits unique sedimentary layers that imply formation through gentle sedimentation. We show that such layering can occur via the gentle sweep-up of material found in the impact plume resulting from the collision of two planetesimals. Such sweep-up requires gas densities consistent with observed transition disks (10-12-10-11 g cm-3). As such, Isheyevo presents the first evidence of our own transition disk and provides new constraints on the evolution of our solar nebula.

Phyllosilicate emission from protoplanetary disks: is the indirect detection of extrasolar water possible?

Phyllosilicates are hydrous minerals formed by interaction between rock and liquid water, and are commonly found in meteorites that originate in the asteroid belt. Collisions between asteroids contribute to zodiacal dust, which therefore reasonably could include phyllosilicates. Collisions between planetesimals in protoplanetary disks may also produce dust that contains phyllosilicates. These minerals possess characteristic emission features in the mid-infrared and could be detectable in extrasolar protoplanetary disks. We have determined whether phyllosilicates in protoplanetary disks are detectable in the infrared, using instruments such as those on board the Spitzer Space Telescope and the Stratospheric Observatory for Infrared Astronomy (SOFIA). We calculated opacities for the phyllosilicates most common in meteorites and, using a two-layer radiative transfer model, computed the emission of radiation from a protoplanetary disk. We found that phyllosilicates present at the 3% level lead to observationally significant differences in disk spectra and should therefore be detectable with the use of infrared observations and spectral modeling. Detection of phyllosilicates in a protoplanetary disk would be diagnostic of liquid water in planetesimals in that disk and would demonstrate similarity to our own Solar System. We also discuss use of phyllosilicate emission to test the "water worlds" hypothesis, which proposes that liquid water in planetesimals should correlate with the inventory of short-lived radionuclides in planetary systems, especially (26)Al.