Real-Time NMR Monitoring of Spatially Segregated Enzymatic Reactions in Multilayered Hydrogel Assemblies*.

Compartmentalized chemical reactions at the microscale are important in biotechnology, yet monitoring the molecular content at these small scales is challenging. To address this challenge, we integrate a compact, reconfigurable reaction cell featuring electrochemical functionality with high-resolution NMR spectroscopy. We demonstrate the operation of this system by monitoring the activity of enzymes immobilized in chemically distinct layers within a multi-layered chitosan hydrogel assembly. As a benchmark, we observed the parallel activities of urease (Urs), catalase (Cat), and glucose oxidase (GOx) by monitoring reagent and product concentrations in real-time. Simultaneous monitoring of an independent enzymatic process (Urs) together with a cooperative process (GOx + Cat) was achieved, with chemical conversion modulation of the GOx + Cat process demonstrated by varying the order in which the hydrogel was assembled.

Broadband stripline Lenz lens achieves 11 × NMR signal enhancement.

A Lenz lens is an electrically passive conductive element that, when placed in a time-varying magnetic field, acts as a magnetic flux concentrator or a magnetic lens. In the realm of nuclear magnetic resonance (NMR), Lenz lenses have been exploited as electrically passive metallic radiofrequency interposers placed between a sample and a tuned or untuned NMR detector in order to focus the [Formula: see text]-field of the detector onto a smaller sample space. Here we explore a novel embodiment of the Lenz lens, which acts as a non-resonant stripline interposer, i.e., the [Formula: see text]-field acts along the longitudinal volume of a sample container, such as a capillary or other microfluidic channel that is coincident with the axis of the stripline. The almost vanishing self-resonance of the stripline Lenz lens, at frequencies relevant for NMR, leads to a desirable [Formula: see text]-field amplitude that is nearly perfectly uniform across the sample and hence lacking a characteristic sinusoidal modal shape. The action of Lenz' law ensures that no stray [Formula: see text]-field is found outside of the stripline's active volume. Because the stripline Lenz lens does not rely on its own geometry to achieve resonance, its frequency response is thus widely broadband for field enhancements up to a factor of 11, with only the external driving resonator properties governing the overall resonant behaviour. We explore the use of the stripline Lenz lens with a sub-nanolitre sample volume, readily detecting 4 isotopes with resonances ranging from 125.76 to 500 MHz. The concept holds potential for the NMR study of thin films, small biological samples, as well as the in situ study of battery materials.

Untuned broadband spiral micro-coils achieve sensitive multi-nuclear NMR TX/RX from microfluidic samples.

The low frequency plateau in the frequency response of an untuned micro-resonator permits broadband radio-frequency reception, albeit at the expense of optimal signal-to-noise ratio for a particular nucleus. In this contribution we determine useful figures of merit for broadband micro-coils, and thereby explore the parametric design space towards acceptable simultaneous excitation and reception of a microfluidic sample over a wide frequency band ranging from 13C to 1H, i.e., 125-500 MHz in an 11.74 T magnet. The detector achieves 37% of the performance of a comparably sized, tuned and matched resonator, and a linewidth of 17 ppb using standard magnet shims. The use of broadband detectors circumvents numerous difficulties introduced by multi-resonant RF detector circuits, including sample loading effects on matching, channel isolation, and field distortion.

An NMR-compatible microfluidic platform enabling in situ electrochemistry.

Combining microfluidic devices with nuclear magnetic resonance (NMR) has the potential of unlocking their vast sample handling and processing operation space for use with the powerful analytics provided by NMR. One particularly challenging class of integrated functional elements from the perspective of NMR are conductive structures. Metallic electrodes could be used for electrochemical sample interaction for example, yet they can cause severe NMR spectral and SNR degradation. These issues are more entangled at the micro-scale since the distorted volume occupies a higher ratio of the sample volume. In this study, a combination of simulation and experimental validation was used to identify an electrode geometry that, in terms of NMR spectral parameters, performs as well as for the case when no electrodes are present. By placing the metal tracks in the side-walls of a microfluidic channel, we found that NMR RF excitation performance was actually enhanced, without compromising B0 homogeneity. Monitoring in situ deposition of chitosan in the microfluidic platform is presented as a proof-of-concept demonstration of NMR characterisation of an electrochemical process.

Broadband and multi-resonant sensors for NMR.

It has always been of considerable interest to study the nuclear magnetic resonance response of multiple nuclei simultaneously, whether these signals arise from internuclear couplings within the same molecule, or from uncoupled nuclei within sample mixtures. The literature contains numerous uncorrelated reports on techniques employed to achieve multi-nuclear NMR detection. This paper consolidates the subset of techniques in which single coil detectors are utilized, and highlights the strengths and weaknesses of each approach, at the same time pointing the way towards future developments in the field of multi-nuclear NMR. We compare the different multi-nuclear NMR techniques in terms of performance, and present a guide to NMR probe designers towards application-based optimum design. We also review the applicability of micro-coils in the context of multi-nuclear methods. Micro-coils benefit from compact geometries and exhibit lower impedance, which provide new opportunities and challenges for the NMR probe designer.

A Non-Resonant Kinetic Energy Harvester for Bioimplantable Applications.

A linear non-resonant kinetic energy harvester for implantable devices is presented. The design contains a metal platform with permanent magnets, two stators with three-dimensional helical coils for increased power generation, ball bearings, and a polydimethylsiloxane (PDMS) package for biocompatibility. Mechanical excitation of this device within the body due to daily activities leads to a relative motion between the platform and stators, resulting in electromagnetic induction. Initial prototypes without packaging have been fabricated and characterized on a linear shaker. Dynamic tests showed that the friction force acting on the platform is on the order of 0.6 mN. The resistance and the inductance of the coils were measured to be 2.2 Ω and 0.4 µH, respectively. A peak open circuit voltage of 1.05 mV was generated per stator at a platform speed of 5.8 cm/s. Further development of this device offers potential for recharging the batteries of implantable biomedical devices within the body.