R. Adam Horch1,2 and John C. Gore1,2
1Vanderbilt University Institute of Imaging Science, Vanderbilt University, Nashville, TN, United States, 2Department of Radiology & Radiological Sciences, Vanderbilt University, Nashville, TN, United States
Synopsis
3D printing is demonstrated as a new means to
fabricate complete RF probeheads for solution-state NMR. Current 3D printing
methods yield mm-scale RF coils with integral sample chambers for
self-contained NMR probes, and 3D-printed microcoils are imminent given ongoing
advances in technology. The unique properties of 3D printing enable facile
construction of potentially thousands of coils at low cost, giving way to dense
coil arrays for high-throughput NMR and novel coil geometries.Introduction and Purpose
Conventional probeheads for solution-state NMR
are constructed using manual
1 or photolithographic techniques
2
that incorporate RF coils, tune/match circuitry, and liquid sample holders into
spatially-compact housings. These techniques are suitable for probeheads with
up to a few 10s of RF coils but suffer from expensive, time consuming, and
labor-intensive manufacturing practices. As an alternative, we have been
exploring stereographic 3D printing that provides rapid, low-cost fabrication
with minimal geometric constraints. 3D printing renders topologically-complex structures
in a wide variety of NMR-compatible polymers, with print resolutions of ~10µm
across build volumes exceeding one cubic meter
3. Herein, we
demonstrate complete, 3D-printed NMR probeheads that contain RF resonators,
variable tuning/matching capacitors, and liquid NMR sample cavities. Fluidically-addressable
channels and cavities are included in the probehead structure, providing a
means for hydraulically-controlled RF tuning/matching and liquid NMR sample
loading/unloading. Electrically conductive RF circuitry is defined within the
3D printed polymer bodies by metallizing certain structures with silver ink. In
this way, multiple independent RF coils and NMR sample cavities can be
fabricated into a single probehead for high-throughput NMR. The unique
scalability of 3D printing supports fabricating thousands of millimeter-scale
coils in a single build session, providing a manufacturing pathway towards a
new generation of low-cost, high-throughput probeheads.
Methods
Stereographic 3D printing utilizes liquid
polymer resins that are photo-crosslinked in a layer-by-layer manner. With a 3D Systems iPro 9000XL Printer using
Somos 11122 Watershed material (DSM Desotech), probeheads were formed with an in-layer resolution of 40 µm and
a through-layer resolution of 150 µm. Probeheads were printed with a number of
non-connecting hollow channels, defining RF circuitry, hydraulic control lines
for variable capacitors, or NMR sample loading pathways. After printing, the RF
circuit channels were selectively metallized by injecting PELCO Silver Paint
(Ted Pella Co.) to form ≈10µm silver coatings for electrically conductive
pathways. In this way, RF-resonant solenoids were constructed and tuned/matched
using parallel-plate variable capacitor networks included in the probehead.
These capacitors contained a partially hollowed dielectric (Figure 1), which
was filled with a variable amount of Fomblin fluorocarbon oil (Solvay Solexis)
or D
2O (99.9%, Sigma Aldrich). Since Fomblin and D
2O are immiscible and have
dielectric constants that differ by 40-fold, a moveable liquid interface
between the two was placed within the capacitor’s dielectric gap to provide
hydraulic control of net capacitance. Additionally, Fomblin and D
2O are
invisible to
1H NMR and bear similar magnetic susceptibility to H
2O, thus
allowing the parallel plate capacitors to be placed in the vicinity of the NMR
sample for a compact RF coil footprint. Probehead sample chambers were filled
with 40 µL saline (1x PBS), and
1H FIDs were collected on a 9.4T Varian/Agilent
small animal imaging system (10kHz BW, 40000 points, 1 acquisition).
Results
Probeheads were successfully printed with
0.75mm-diameter hollow channels to define RF coils, each consisting of a
5mm-diameter/5-turn solenoid and three parallel-plate capacitors for
tuning/matching (Figure 2). The complete RF coil circuit occupied a 2 mL
footprint, which was printed into an 8mL probehead body with fluid couplings for
separate hydraulic control of the capacitors and NMR sample (Figure 3). RF
bench testing showed a broad tuning range of 40 MHz as the capacitors were hydraulically
varied, with Q ≈ 10 at 400 MHz (Figure 4). A match of only -12dBm (S
11) could be
achieved at 400 MHz, and efforts are underway to optimize coil geometry and
capacitor range for an improved match. However,
1H FIDs on 40 µL saline were
observed at 400 MHz (Figure 5), with a ≈ 20 Hz linewidth acceptable for
high-throughput NMR processes such as drug screening. The coil gave a 1 kHz
nutation rate under 125 mW input RF power, indicating compatibility with
low-cost, low-power RF front-end electronics.
Discussion and Conclusions
3D printing and selective silvering was demonstrated
as a new means to fabricate complete NMR probeheads for solution-state NMR. Importantly,
RF coil tuning/matching and NMR sample loading/unloading could both be
controlled hydraulically, which is compatible with high-throughput
infrastructure from the microfluidics industry. Recently-developed 3D printers
have driven the minimum build resolutions to 5-fold smaller than what was used
herein, so work is now underway to fabricate single probeheads with high-density
arrays of independent RF coils and NMR sample pathways. Ultimately, the
metallizing process will be combined with the 3D-printing process for facile
construction of large numbers of coils. Given its low cost and build
scalability, 3D printing offers a unique means to construct probeheads of
unprecedented complexity, enabling drastically denser arrays for
high-throughput NMR and novel coil geometries that are not available with
conventional fabrication techniques.
Acknowledgements
Vanderbilt University Department of Radiology,
NIH T32 EB001628.References
1) e.g. Webb, A. G. Progress in Nuclear
Magnetic Resonance Spectroscopy 31, 1–42 (1997).
2) e.g. Lee, H., Sun, E., Ham, D. and
Weissleder, R. Nat Med 14, 869–874 (2008).
3) see manufacturer
specifications at www.stratasys.com and www.3dsystems.com