The longitudinal relaxation time (termed as T 1 ) of nitrogen-vacancy (NV) centers in nanodiamonds can be affected by surface electric or magnetic noise, which has been exploited to develop cutting-edge quantum relaxometry for biochemical sensing. In this work, a tiny all-fiber quantum probe based on longitudinal relaxometry was developed by chemically-anchoring nanodiamonds on the surface of a cone fiber tip. The dependences of T 1 on surface electric and magnetic noise were discussed in theories first and then experimentally demonstrated in varied pH and Gd 3+ concentration solutions, respectively. Because of NV centers being subject to enhanced coupling from surface noise, T 1 reduced from 290 to 245 µs when pH changed from 3 to 9 and reduced to 220 µs when Gd 3+ concentration increased to 10 mM, agreeing well with theoretical results. Based on these, the Gd 3+ -tagged-biotin and streptavidin model was designed and implemented on the all-fiber probe, and results demonstrated the detection of biotin with a limit of 168 nM and good specificity. This paper opens a new way to develop an all-fiber quantum probe by exploiting the unique electrical spin properties of NV centers, and the probe shows great potential for biological detection with high sensitivity and specificity.
The longitudinal relaxation time (termed as T 1 ) of nitrogen-vacancy (NV) centers in nanodiamonds can be affected by surface electric or magnetic noise, which has been exploited to develop cutting-edge quantum relaxometry for biochemical sensing. In this work, a tiny all-fiber quantum probe based on longitudinal relaxometry was developed by chemically-anchoring nanodiamonds on the surface of a cone fiber tip. The dependences of T 1 on surface electric and magnetic noise were discussed in theories first and then experimentally demonstrated in varied pH and Gd 3+ concentration solutions, respectively. Because of NV centers being subject to enhanced coupling from surface noise, T 1 reduced from 290 to 245 µs when pH changed from 3 to 9 and reduced to 220 µs when Gd 3+ concentration increased to 10 mM, agreeing well with theoretical results. Based on these, the Gd 3+ -tagged-biotin and streptavidin model was designed and implemented on the all-fiber probe, and results demonstrated the detection of biotin with a limit of 168 nM and good specificity. This paper opens a new way to develop an all-fiber quantum probe by exploiting the unique electrical spin properties of NV centers, and the probe shows great potential for biological detection with high sensitivity and specificity.
The investigation of biomolecular interactions at the single-molecule level has emerged as a pivotal research area in life science, particularly through optical, mechanical, and electrochemical approaches. Spins existing widely in biological systems, offer a unique degree of freedom for detecting such interactions. However, most previous studies have been largely confined to ensemble-level detection in the spin degree. Here, we developed a molecular interaction analysis method approaching single-molecule level based on relaxometry using the quantum sensor, nitrogen-vacancy (NV) center in diamond. Experiments utilized an optimized diamond surface functionalized with a polyethylenimine nanogel layer, achieving $\sim$10 nm average protein distance and mitigating interfacial steric hindrance. Then we measured the strong interaction between streptavidin and spin-labeled biotin complexes, as well as the weak interaction between bovine serum albumin and biotin complexes, at both the micrometer scale and nanoscale. For the micrometer-scale measurements using ensemble NV centers, we re-examined the often-neglected fast relaxation component and proposed a relaxation rate evaluation method, substantially enhancing the measurement sensitivity. Furthermore, we achieved nanoscale detection approaching single-molecule level using single NV centers. This methodology holds promise for applications in molecular screening, identification and kinetic studies at the single-molecule level, offering critical insights into molecular function and activity mechanisms.
Nanoscale quantum probes such as the nitrogen-vacancy (NV) center in diamonds have demonstrated remarkable sensing capabilities over the past decade as control over fabrication and manipulation of these systems has evolved. The biocompatibility and rich surface chemistry of diamonds has added to the utility of these probes but, as the size of these nanoscale systems is reduced, the surface chemistry of diamond begins to impact the quantum properties of the NV center. In this work, we systematically study the effect of the diamond surface chemistry on the quantum coherence of the NV center in nanodiamonds (NDs) 50 nm in size. Our results show that a borane-reduced diamond surface can on average double the spin relaxation time of individual NV centers in nanodiamonds when compared to thermally oxidized surfaces. Using a combination of infrared and X-ray absorption spectroscopy techniques, we correlate the changes in quantum relaxation rates with the conversion of sp 2 carbon to C–O and C–H bonds on the diamond surface. These findings implicate double-bonded carbon species as a dominant source of spin noise for near surface NV centers. The link between the surface chemistry and quantum coherence indicates that through tailored engineering of the surface, the quantum properties and magnetic sensitivity of these nanoscale systems may approach that observed in bulk diamond.
Quantum sensing using nitrogen-vacancy (NV) centers in diamond has emerged as a powerful platform for detecting ultra-low magnetic fields under ambient conditions. Owing to their long spin coherence times, optical addressability, and compatibility with aqueous environments, it has found widespread applications in biosensing and bio-imaging. This review presents the fundamental principles and recent advances in NV-based quantum magnetometry for biosensing applications, with a particular focus on measurements in aqueous medium and at cellular and molecular length scales. We discuss the underlying spin physics of NV centers and highlight two primary detection modalities: optically detected magnetic resonance (ODMR) and T1 relaxometry-based sensing and how these approaches aids in the detection of both static magnetic fields and dynamic magnetic noise arising from biological processes. The review explores key application areas, including nanoscale nuclear magnetic resonance (NMR), monitoring of neural activity, detection of abnormal or rogue cells using NV-based platforms etc. In addition, strategies for enhancing sensitivity, such as surface functionalization of nanodiamonds, femtosecond (fs) laser-written photonic structures, and integration with microfluidic and lab-on-chip systems have also been discussed in depth. We also address the critical challenges, including surface-induced decoherence, charge-state instability, and signal-to-noise limitations in biofluids associated with NV-based biosensing applications. Finally, we outline future prospects, highlighting how NV-based magnetic biosensing provides a promising pathway for translating quantum sensing technologies into practical biomedical applications.
Efficient collection of photoluminescence arising from spin dynamics of nitrogen vacancy (NV) centers in diamond is important for practical applications involving precise magnetic field or temperature mapping. These goals may be realized by the integration of nanodiamond particles with optical fibers and volumetric doping of the particles alongside the fiber core. That approach combines the advantages of robust axial fixation of NV diamonds with a direct spatial overlap of their fluorescence with the guided mode of the fiber. We developed a suspended core silicate glass fiber with 750 nm-diameter nanodiamonds located centrally in the 1.5 µm-core cross-section along its axis. The developed fiber probe was tested for its magnetic sensing performance in optically detected magnetic resonance measurements using a 24 cm-long fiber sample, with the NV excitation and fluorescence collection from the far ends of the sample and yielding optical readout contrast of 7% resulting in 0.5 µT·Hz-1/2 magnetic field sensitivity, two orders of magnitude better than in earlier designs. Thanks to its improved fluorescence confinement, the developed probe could find application in magnetic sensing over extended fiber length, magnetic field mapping or gradiometry.
The NV defect center in diamond forms a pseudo-atomic quantum system with discreet optically excitable transitions between ground and excited states in the gap between valence and conduction bands, making the NV center a deep-level defect center in diamond. For the negatively charged NV center (NV-), both the ground and excited states are spin triplets (S=1) and coupling between optical and spin states provides unique opportunities for optical detection of magnetic resonance (ODMR) and quantum metrology under ambient conditions. As an atomically sized point defect that is stable in single nanodiamonds as small as a few nanometers, the NV center enables spin based imaging of temperature, electric fields, magnetic fields and mechanical strain with nanoscale spatial resolution. Made of carbon, nanodiamonds are also ideal nanoparticles for use in biological systems, exhibiting extremely low cytotoxicity, no photo bleaching and exceptional contrast in transmission electron and light microscopy. With the ability to act as both a passive, non perturbing sensor (e.g. a diamagnetic material used for sensing magnetic fields) and a connection point for two way, direct coupling of far field optics to NV− spins and indirectly to the highly localized neighborhood of atoms, electronic states and phonon modes in the local vicinity, NV diamond provides a route to nanoscale field sensing and spin based optical microscopy. These sensors are also stable in nanodiamonds. For nanoparticles, the reduction in particle diameter dramatically enhances the proportion of the material that is surface exposed, enhancing any surface related properties. Nitrogen Vacancy centers in nanodiamonds provide another example of material properties that vary with particle size. In chapter 5, evidence that modulation of nanodiamonds fluorescent emissions by electrical perturbations in their surrouding environment allows transduction of local electrodynamics into a far field optical signal capable of mapping action potentials in cardiomyocytes in presented. The unifying theme for all of the work presented in this dissertation is to enable the use of magnetic resonance signals and interactions for imaging and sensing in previously inaccessible regimes. The specific focus is on methods and techniques to enable nanoscale physical sensing and functional imaging in live tissues, with the ultimate aim to lay the predicate for the combination of both without compromise.
The negatively charged nitrogen-vacancy (NV) center in diamond has emerged as a powerful and versatile quantum sensor for diverse quantities.In particular, all-optical diamond based relaxometry (or T1), which consists of monitoring the NV centers' photoluminescence submitted to a train of green laser pulses, allows to detect magnetic noise and its origin.When applied on diamond nanoparticles, it allows nanoscale resolution and has many applications in biology, for monitoring chemical reactions metabolic activity or diagnostic markers.While increasing the number of NV centers in a nanodiamond allows to collect more signal, a standardized method to extract information from relaxometry experiments of such NV ensembles is still missing.In this article, we use a set of T1 relaxation curves acquired at different concentrations of gadolinium ions to calibrate and optimize the entire data processing flow, from the acquired raw data to the extracted T1.In particular, we use a bootstrap to derive a signal to noise ratio that can be quantitatively compared from one method to another.At first, T1 curves are extracted from photoluminescence pulses.We compare integrating their signal through an optimized window as performed conventionally, to fitting a known function on it.Fitting the decaying T1 curves allows to obtain the relevant T1 value.We compared here the three most commonly used fit models that are, single, bi, and stretched-exponential.We finally investigated the effect of the bootstrap itself on the precision of the result as well as the use of a rolling window to allows time-resolution.