Reactively sputtered nickel oxide (NiOx) films provide transparent, antireflective, electrically conductive, chemically stable coatings that also are highly active electrocatalysts for the oxidation of water to O2(g). These NiOx coatings provide protective layers on a variety of technologically important semiconducting photoanodes, including textured crystalline Si passivated by amorphous silicon, crystalline n-type cadmium telluride, and hydrogenated amorphous silicon. Under anodic operation in 1.0 M aqueous potassium hydroxide (pH 14) in the presence of simulated sunlight, the NiOx films stabilized all of these self-passivating, high-efficiency semiconducting photoelectrodes for >100 h of sustained, quantitative solar-driven oxidation of water to O2(g).
We show that high-resolution NMR can reach picomole sensitivity for micromolar concentrations of analyte by combining parahydrogen induced hyperpolarisation (PHIP) with a high-sensitivity transmission line micro-detector. The para-enriched hydrogen gas is introduced into solution by diffusion through a membrane integrated into a microfluidic chip.NMR microdetectors, operating with sample volumes of a few µL or less, benefit from a favourable scaling of mass sensitivity. However, the small volumes make it very difficult to detect species present at less than millimolar concentrations in microfluidic NMR systems.In view of overcoming this limitation, we implement parahydrogen-induced polarisation (PHIP) on a microfluidic device with 2.5 µL detection volume. Integrating the hydrogenation reaction into the chip minimises polarisation losses to spin-lattice relaxation, allowing the detection of picomoles of substance. This corresponds to a concentration limit of detection of better than 1 µM √ s, unprecedented at this sample volume. The stability and sensitivity of the system allows quantitative characterisation of the signal dependence on flow rates and other reaction parameters and permits homo-( 1 H-1 H) and heteronuclear( 1 H-13 C) 2D NMR experiments at natural 13 C abundance.
Silicon photoanodes patterned with thin-film Ni catalyst islands exhibited stable sunlight-driven O2 evolution for over 240 h of continuous operation in 1.0 M KOH.
We present a quantitative study of the metabolic activity of a single spheroid culture of human cancer cells. NMR (nuclear magnetic resonance) spectroscopy is an ideal tool for observation of live systems due to its non-invasive nature. However, limited sensitivity has so far hindered its application in microfluidic culture systems. We have used an optimised micro-NMR platform to observe metabolic changes from a single spheroid. NMR spectra were obtained by directly inserting microfluidic devices containing spheroids ranging from 150 $$\upmu$$
μ
m to 300 $$\upmu$$
μ
m in diameter in 2.5 $$\upmu$$
μ
L of culture medium into a dedicated NMR probe. Metabolite concentrations were found to change linearly with time, with rates approximately proportional to the number of cells in the spheroid. The results demonstrate that quantitative monitoring of a single spheroid with $$\le$$
≤
2500 cells is possible. A change in spheroid size by 600 cells leads to a clearly detectable change in the l-Lactic acid production rate ($$p=3.5\times 10^{-3}$$
p
=
3.5
×
10
-
3
). The consumption of d-Glucose and production of l-Lactic acid were approximately 2.5 times slower in spheroids compared to monolayer culture of the same number of cells. Moreover, while cells in monolayer culture were found to produce l-Alanine and l-Glutamine, spheroids showed slight consumption in both cases.
Side‐arm hydrogenation (SAH) by homogeneous catalysis has extended the reach of the parahydrogen enhanced NMR technique to key metabolites such as pyruvate. However, homogeneous hydrogenation requires rapid separation of the dissolved catalyst and purification of the hyperpolarised species with a purity sufficient for safe in‐vivo use. An alternate approach is to employ heterogeneous hydrogenation in a continuous‐flow reactor, where separation from the solid catalysts is straightforward. Using a TiO2‐nanorod supported Rh catalyst, we demonstrate continuous‐flow parahydrogen enhanced NMR by heterogeneous hydrogenation of a model SAH precursor, propargyl acetate, at a flow rate of 1.5 mL/min. Parahydrogen gas was introduced into the flowing solution phase using a novel tube‐in‐tube membrane dissolution device. Without much optimization, proton NMR signal enhancements of up to 297 (relative to the thermal equilibrium signals) at 9.4 Tesla were shown to be feasible on allyl‐acetate at a continuous total yield of 33 %. The results are compared to those obtained with the standard batch‐mode technique of parahydrogen bubbling through a suspension of the same catalyst.
Microfluidic systems hold great potential
for the study of live
microscopic cultures of cells, tissue samples, and small organisms.
Integration of hyperpolarization would enable quantitative studies
of metabolism in such volume limited systems by high-resolution NMR
spectroscopy. We demonstrate, for the first time, the integrated generation
and detection of a hyperpolarized metabolite on a microfluidic chip.
The metabolite [1-
13
C]fumarate is produced in a nuclear
hyperpolarized form by (i) introducing para-enriched hydrogen into
the solution by diffusion through a polymer membrane, (ii) reaction
with a substrate in the presence of a ruthenium-based catalyst, and
(iii) conversion of the singlet-polarized reaction product into a
magnetized form by the application of a radiofrequency pulse sequence,
all on the same microfluidic chip. The microfluidic device delivers
a continuous flow of hyperpolarized material at the 2.5 μL/min
scale, with a polarization level of 4%. We demonstrate two methods
for mitigating singlet–triplet mixing effects which otherwise
reduce the achieved polarization level.
A generic approach is presented that allows high-resolution NMR spectroscopy of water/oil droplet emulsions in microfluidic devices. Microfluidic NMR spectroscopy has recently made significant advances due to the design of micro-detector systems and their successful integration with microfluidic devices. Obtaining NMR spectra of droplet suspensions, however, is complicated by the inevitable differences in magnetic susceptibility between the chip material, the continuous phase, and the droplet phases. This leads to broadening of the NMR resonance lines and results in loss of spectral resolution. We have mitigated the susceptibility difference between the continuous (oil) phase and the chip material by incorporating appropriately designed air-filled structures into the chip. The susceptibilities of the continuous and droplet (aqueous) phases have been matched by doping the droplet phase with a Eu3+ complex. Our results demonstrate that this leads to a proton line width in the droplet phase of about 3 Hz, enabling high-resolution NMR techniques.
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