Single chip dynamic nuclear polarization microsystem

Integration of the sensitivity-relevant electronics of nuclear magnetic resonance (NMR) and electron spin resonance (ESR) spectrometers on a single chip is a promising approach to improve the limit of detection, especially for samples in the nanoliter and subnanoliter range. Here, we demonstrate the cointegration on a single silicon chip of the front-end electronics of NMR and ESR detectors. The excitation/detection planar spiral microcoils of the NMR and ESR detectors are concentric and interrogate the same sample volume. This combination of sensors allows one to perform dynamic nuclear polarization (DNP) experiments using a single-chip-integrated microsystem having an area of about 2 mm2. In particular, we report 1H DNP-enhanced NMR experiments on liquid samples having a volume of about 1 nL performed at 10.7 GHz(ESR)/16 MHz(NMR). NMR enhancements as large as 50 are achieved on TEMPOL/H2O solutions at room temperature. The use of state-of-the-art submicrometer integrated circuit technologies should allow the future extension of the single-chip DNP microsystem approach proposed here up the THz(ESR)/GHz(NMR) region, corresponding to the strongest static magnetic fields currently available. Particularly interesting is the possibility to create arrays of such sensors for parallel DNP-enhanced NMR spectroscopy of nanoliter and subnanoliter samples.

Dynamic nuclear polarisation via the integrated solid effect II: experiments on naphthalene-h(8) doped with pentacene-d(14)

Tim Rolf Eichhorn

In dynamic nuclear polarisation (DNP), also called hyperpolarisation, a small amount of unpaired electron spins is added to the sample containing the nuclear spins, and the polarisation of these unpaired electron spins is transferred to the nuclear spins by means of a microwave field. Traditional DNP polarises the electron spin of stable paramagnetic centres by cooling down to low temperature and applying a strong magnetic field. Then weak continuous wave microwave fields are used to induce the polarisation transfer. Complicated cryogenic equipment and strong magnets can be avoided using short-lived photo-excited triplet states that are strongly aligned in the optical excitation process. However, a much faster transfer of the electron spin polarisation is needed and pulsed DNP methods like nuclear orientation via electron spin locking (NOVEL) and the integrated solid effect (ISE) are used. To describe the polarisation transfer with the strong microwave fields in NOVEL and ISE, the usual perturbation methods cannot be used anymore. In the previous paper, we presented a theoretical approach to calculate the polarisation transfer in ISE. In the present paper, the theory is applied to the system naphthalene-h(8) doped with pentacene-d(14) yielding the photo-excited triplet states and compared with experimental results.

Taylor & Francis2014

Nanoscale Magnetometry with Single Fluorescent Nanodiamonds Manipulated in an Anti-Brownian Electrokinetic Trap

Metin Kayci

Studies on single-molecule spectroscopy and nanoscale detection have been remarkably driven by an interest to reveal quantum and conformational states of single particles, the intra-molecular dynamics and their response to physical observables hidden by ensemble level measurements. A straightforward practice used in enhancing the signal from single particles is either to immobilize them on an engineered substrate or to embed them in a solid matrix. Given that the biophysical properties of the host environment introduce new perturbations and the particles will not behave as in their native environment, such approaches are inefficient to reflect the real dynamics. Therefore, recent advances in the field of single-molecule have led to a renewed interest in novel trapping methods, increased efforts into the development of promising tools for extended investigation, and the manipulation of solution-phase bio-molecules in real time. Despite the variety of successful passive trapping techniques, precise manipulation through non-perturbative forces is a big challenge for nano-sized particles. Such techniques either exert high power to the sample or compel special operating conditions disturbing the native environment. Therefore, an active trapping scheme guiding non-perturbative forces can break the trade-off between the particle size and the excreted power. This dissertation presents the development of an active trapping set-up using non-perturbative electrokinetic feedback and demonstrates its performance on nano-sized single particles for aims in biophysics. The essential theme is the engineering aspect of the technique, including the feedback configurations for various fluidic devices, the corresponding particle tracking schemes and the integration of the trapping platform to an integrated circuit pattern for advanced manipulation aims. The second theme is on specialized single fluorescence nanodiamonds (FNDs) as scanning magnetometer in fluidics. The implemented active trapping tool is employed for the manipulation of a rotationally free single FND to detect the localized magnetic field through an optically detected magnetic resonance (ODMR) spectrum. While the laser beam used in particle tracking can serve in optical excitation, an external radio frequency (RF) source is not sufficient to achieve microwave manipulation. Therefore, an RF antenna is designed to transmit the microwave signal to the proximity of the trapping chamber for electron spin resonance (ESR) spectroscopy. A nanostage positioning controller introduces scanning ability to the sample plane, in relative position of the trapped particle, in order to map the distribution of the detected fields over a fluidic volume. As FNDs are also sensitive to many other physical quantities, nanoscale single particle trapping and diamond photonics linkages are realized in this work, which provide an outstanding alternative for detection and imaging in complex fluidic environments that are closed to AFM-like physically supported probes.

EPFL2016

Methods and microfabrication techniques for subnanoliter magnetic resonance spectroscopy

Enrica Montinaro

Nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and ferromagnetic resonance (FMR) spectroscopy can open up the possibility of studying many scientifically and biologically relevant samples at the µm and sub-µm scale. Examples of volume-limited systems include numerous species of microorganisms, mammalian zygotes, the majority of cells, proteins limited in growth, micro and nanostructured devices for the analysis of spin dynamics at the sub-µm scale. These volume-limited samples cannot be addressed by commercially available inductive spectrometers due to their constraint in sensitivity. It was previously proposed in our group that CMOS technology can be used to realize miniaturized high sensitivity inductive detection systems, having spin sensitivities at least two orders of magnitude greater than the commercially available spectrometers. During my PhD work, I developed methods and microfabrication techniques to perform NMR, EPR and FMR spectroscopy at the µm and sub-µm scale by using high sensitivity single chip CMOS detectors, previously proposed in our group. Microfluidic systems for the non-invasive handling of liquid samples and biological entities immersed in liquids are realized and integrated with the CMOS single chip NMR and EPR detectors. Microfluidic channels are fabricated via conventional microfabrication techniques and via two-photon polymerization, a 3D printing technique with a lateral resolution of 300 nm. The 3D printing technique is found to be an exceptional solution for NMR applications. Due to the flexibility in the design of the microfluidic systems, it is possible to reduce the magnetic field non-uniformieties with a consequent improval in spectral resolution. Spectral resolutions down to 0.007 ppm are reported for liquids having sample volumes of 100 pL. For the first time, NMR studies on intact biological entities submerged in liquid media of choice are performed, using 3D printed microfluidic systems. A spin sensitivity of 2.5·1013 spins/¿Hz is shown, sufficient to detect highly concentrated endogenous compounds in active volumes down to 100 pL with measurement times down to 3 h. EPR measurements on subnanoliter liquids and frozen solutions are reported, by the combination of commercially available capillaries and EPR single chip detectors. This is a first but important step towards the study of biological samples, whose paramagnetic ions have relaxation times too short to be measured at room temperature. Moreover, a novel method for the sensing of magnetic microbeads is presented, which is based on the detection of the change of susceptibility in FMR condition by the CMOS integrated detector. Due to the frequency and field dependence of the susceptibility, the detected variation is 20 times greater than the change in magnetization measured in static conditions by other approaches. The proposed detection scheme allows for single bead sensitivity over an active area of about 5·104 µm2. Lastly, sub-µm scale FMR detection capabilities of the single chip CMOS detector are shown by experiments on nanopatterned single permalloy (80% Ni - 20% Fe) and YIG (Yittrium Iron Garnet) dots. The combination of high sensitivity and large active area is seen as a considerable advantage with respect to other FMR detection methods, which suffer either from sensitivity or from reduced active area.