9 research outputs found
Photoinitiated Dynamics in Amorphous Solid Water via Nanoimprint Lithography
Laser pulses that act on fragile
samples often alter them irreversibly,
motivating single-pulse data collection. Amorphous solid water (ASW)
is a good example. In addition, neither well-defined paths for molecules
to travel through ASW nor sufficiently small samples to enable molecular
dynamics modeling have been achieved. Combining nanoimprint lithography
and photoinitiation overcomes these obstacles. An array of gold nanoparticles
absorbs pulsed (10 ns) 532 nm radiation and converts it to heat, and
doped ASW films grown at about 100 K are ejected from atop the irradiated
nanoparticles into vacuum. The nanoparticles are spaced from one another
by sufficient distance that each acts independently. Thus, a temporal
profile of ejected material is the sum of about 10<sup>6</sup> “nanoexperiments,”
yielding high single-pulse signal-to-noise ratios. The size of a single
nanoparticle and its immediate surroundings is sufficiently small
to enable modeling and simulation at the atomistic (molecular) level,
which has not been feasible previously. An application to a chemical
system is presented in which H/D scrambling is used to infer the presence
of protons in films composed of D<sub>2</sub>O and H<sub>2</sub>O
(each containing a small amount of HDO contaminant) upon which a small
amount of NO<sub>2</sub> has been deposited. The pulsed laser heating
of the nanoparticles promotes NO<sub>2</sub>/N<sub>2</sub>O<sub>4</sub> hydrolysis to nitric acid, whose protons enhance H/D scrambling
dramatically
Amorphous Solid Water: Pulsed Heating of Buried N<sub>2</sub>O<sub>4</sub>
Molecular
transport and morphological change were examined in films
of amorphous solid water (ASW). A buried N<sub>2</sub>O<sub>4</sub> layer absorbs pulsed 266 nm radiation, creating heated fluid. Temperature
and pressure gradients facilitate the formation of fissures through
which fluid travels to (ultrahigh) vacuum. Film thickness up to 2400
monolayers was examined. In all cases, transport to vacuum could be
achieved with a single pulse. Material that entered vacuum was detected
using a time-of-flight mass spectrometer that recorded spectra every
10 μs. An ASW layer insulated the N<sub>2</sub>O<sub>4</sub> layer from the high-thermal-conductivity MgO substrate; this was
verified experimentally and with heat-transfer calculations. Laser-heated
fluid strips water from fissure walls throughout its trip to vacuum.
Experiments with alternate H<sub>2</sub>O and D<sub>2</sub>O layers
reveal efficient isotope scrambling, consistent with water reaching
vacuum via this mechanism. It is likely that ejected water undergoes
collisions just above the film surface due to the high density of
material that reaches the surface via fissures, as evidenced by complex
temporal profiles extending past 1 ms. Little material enters vacuum
after cessation of the 10 ns pulse because cold ASW near the film
surface freezes material that is no longer being heated. A proposed
model is in accord with the data
Example of a portion of an array with a box pattern of electrodes used for deprotection and synthesis with varying concentrations of base during the deprotection step.
<p>Note that the central electrode and electrodes surrounding the box are not active during deprotection and so should not have any synthesis occurring over them.</p
Results from the cloning and sequencing of DNA removed from the microarray.
<p>Results from the cloning and sequencing of DNA removed from the microarray.</p
Example of a portion of an array with a box pattern of electrodes used for deprotection and synthesis at 0.4, 0.7, 1.0 and 1.4 micro amp/electrode.
<p>Example of a portion of an array with a box pattern of electrodes used for deprotection and synthesis at 0.4, 0.7, 1.0 and 1.4 micro amp/electrode.</p
Example of a portion of an array demonstrating a voltage study from 1.2 to 2.4 V.
<p>Example of a portion of an array demonstrating a voltage study from 1.2 to 2.4 V.</p
The design of the linker used in this experiment
<p>The design of the linker used in this experiment</p