Polarization Buildup Research Articles

Development of a fully automated workstation for conducting routine SABRE hyperpolarization

SABRE is emerging as a fast, simple and low-cost hyperpolarization method because of its ability to regenerate enhanced NMR signals. Generally, SABRE hyperpolarization has been performed predominantly manually, leading to variations in reproducibility and efficiency. Recent advances in SABRE include the development of automated shuttling systems to address previous inconsistencies. However, the operational complexity of such systems and the challenges of integration with existing workflows hinder their widespread adoption. This work presents a fully automated lab workstation based on a benchtop NMR spectrometer, specifically designed to facilitate SABRE of different nuclei across different polarization fields. We demonstrated the capability of this system through a series of routine SABRE experimental protocols, including consecutive SABRE hyperpolarization with high reproducibility (average standard deviation of 1.03%), optimization polarization of 13C nuclei respect to the polarization transfer field, and measurement of polarization buildup rate or decay time across a wide range of magnetic fields. Furthermore, we have iteratively optimized the durations for pulsed SABRE-SHEATH 13C pyruvate. The constructed SABRE workstation offers full automation, high reproducibility, and functional diversification, making it a practical tool for conducting routine SABRE hyperpolarization experiments. It provides a robust platform for high-throughput and reliable SABRE and X-SABRE hyperpolarization studies.

Maximizing Relayed 1H Hyperpolarization Transfer by Slow-Fast MAS NMR Spectroscopy.

1H-detected dynamic nuclear polarization (DNP)-enhanced fast magic angle spinning (MAS) NMR experiments provide unprecedented sensitivity to study the structure and dynamics in advanced materials and biomolecules. However, in relayed DNP experiments, DNP enhancements decrease with faster MAS rates, which is detrimental for sensitivity. The decrease is because 1H-1H spin diffusion rates are significantly reduced at fast MAS frequencies. To improve sensitivity at these fast MAS rates, here, we propose to combine fast polarization build-up by relay at slow MAS rate with high-resolution 1H NMR at fast MAS for acquisition. We perform experiments on l-histidine·HCl·H2O with MAS rates of up to 65 kHz using a 0.7 mm DNP probe at 18.8 T and 100 K. We obtain a 35% improvement in sensitivity in experiments where the sample is polarized at 20 kHz MAS and where the signal is acquired at 60 kHz MAS.

Giant hyperfine interaction between a dark exciton condensate and nuclei.

We study the interaction of a dark exciton Bose-Einstein condensate with the nuclei in gallium arsenide/aluminum gallium arsenide coupled quantum wells and find clear evidence for nuclear polarization buildup that accompanies the appearance of the condensate. We show that the nuclei are polarized throughout the mesa area, extending to regions that are far away from the photoexcitation area and persisting for seconds after the excitation is switched off. Photoluminescence measurements in the presence of radio frequency radiation reveal that the hyperfine interaction between the nuclear and electron spins is enhanced by two orders of magnitude. We suggest that this large enhancement manifests the collective nature of the N-exciton condensate, which amplifies the interaction by a factor of [Formula: see text].

Studies of the spin coherence time of protons at COSY

The search for the Electric Dipole Moments (EDM) of charged particles in storage rings necessitates polarized beams with long Spin Coherence Time (SCT) of the circulating beam. The SCT is the time during which the RMS spread of the orientation of spins of all particles in the bunch reaches one radian. A long SCT is needed to observe the coherent effect of a polarization build-up induced by the EDM. For deuterons the SCT of 1000 s has been achieved at the COoler SYnchrotron COSY (Jülich, Germany). Accomplishing such long SCT for protons is far more challenging due to their higher anomalous magnetic moment, but essential for the planned EDM experiments. It has been shown that for protons the SCT is strongly influenced by nearby intrinsic and integer spin resonances. The strengths of the latter have been calculated for a typical optics setting of COSY and the overall influence on the SCT was predicted. In addition, the efficiency of proton spin flipping with an RF solenoid from initially vertical direction into the ring plane is also investigated.

Optimisation of dynamic nuclear polarisation using "off-the-shelf" Gd(III)-based polarising agents.

Complexes of paramagnetic metal ions, in particular Gd3+, have been demonstrated as efficient polarising agents for magic-angle spinning (MAS) dynamic nuclear polarisation (DNP). We recently demonstrated that commercially available and inexpensive Gd(NO3)3 is suitable for use as an "off-the-shelf" MAS DNP polarising agent, providing promising sensitivity enhancements to 1H, 13C, and 15N NMR signals. Here we expand upon this approach by investigating the impact of the Gd(NO3)3 concentration and by exploring a larger range of readily available Gd3+ sources. We found that a Gd(NO3)3 concentration of 20 mM in the case of 1H and 13C, and 40 mM in the case of 15N, offers optimum signal enhancements and is rationalised as a trade-off between DNP enhancements, polarisation build-up times, and electron paramagnetic resonance (EPR) spin-spin relaxation times. We determined that a range of different gadolinium compounds (GdCl3, Gd2(SO4)3, GdBr3, and Gd(OAc)3) are also suitable for use as polarising agents and yield 1H, 13C, and 15N signal enhancements of variable values. Gd(OAc)3 yields lower signal enhancements, which is proposed to be the result of greater local asymmetry at the Gd3+ centre leading to EPR line broadening, and the methyl group in the acetate ion acting as a relaxation sink and limiting the nuclear polarisation available.

Quantitative Analysis in Continuous-Flow ^1H Benchtop NMR Spectroscopy by Paramagnetic Relaxation Enhancement

Nuclear magnetic resonance (NMR) spectroscopy is an excellent tool for reaction and process monitoring. Process monitoring is often carried out online, where the analytic device is operated in flow mode. Benchtop NMR spectrometers are especially well-suited for these applications because they can be installed close to the studied process. However, quantitative analysis of a fast-flowing liquid with NMR spectroscopy is challenging because short residence times in the magnetic field of the spectrometer result in inefficient polarization buildup and thus poor signal intensity. This is particularly problematic for benchtop NMR spectrometers, where it severely limits the flow velocity in quantitative measurements. One method for increasing polarization in continuous-flow NMR spectroscopy is paramagnetic relaxation enhancement (PRE). Here, the interaction of the studied liquid with a PRE agent significantly accelerates the buildup of nuclear polarization prior to NMR detection, which enables quantitative measurements at high flow velocities. For process monitoring applications, the synthesis of robust and chemically inert immobilized PRE agents is mandatory. This was accomplished in the present work, where a new PRE agent is tested on 12 common solvents including water, acetonitrile, 1,4-dioxane, and binary mixtures with quantitative benchtop ^1H NMR spectroscopy at 1 Tesla. The results show that the flow regime for quantitative measurements can be greatly extended by the use of the synthesized PRE agent.

Multi-Contaminant Getter for Trace Airborne Contaminant Capture in Elevated Temperature Electrochemical Systems

Electrochemical systems operating at elevated temperatures such as solid oxide fuel cells (SOFC), solid oxide electrolysis cells (SOEC) and oxygen transport membranes (OTM) are susceptible to electrochemical performance degradation due to the presence of intrinsic and extrinsic contaminants in air stream. Intrinsic and extrinsic airborne contaminants include a wide range of gaseous compounds consisting of cations such as Cr, Si, and B, intrinsic impurities include SOx, NOx, VOC and PM’s. During high temperature exposure, the contaminants deposit and react with the cell components leading to both ohmic and non-ohmic polarization buildup. The use of a cost-effective, design-agnostic, passive “getter” system has been proposed for capturing trace contaminants. A number of getter formulations (containing alkaline earth, transition metal and lanthanide group elements) have been synthesized and experimentally tested. Results will be presented.

Modelling and correcting the impact of RF pulses for continuous monitoring of hyperpolarized NMR.

Monitoring the build-up or decay of hyperpolarization in nuclear magnetic resonance requires radio-frequency (RF) pulses to generate observable nuclear magnetization. However, the pulses also lead to a depletion of the polarization and, thus, alter the spin dynamics. To simulate the effects of RF pulses on the polarization build-up and decay, we propose a first-order rate-equation model describing the dynamics of the hyperpolarization process through a single source and a relaxation term. The model offers a direct interpretation of the measured steady-state polarization and build-up time constant. Furthermore, the rate-equation model is used to study three different methods to correct the errors introduced by RF pulses: (i)a correction ( denoting the RF pulse flip angle), which is only applicable to decays; (ii)an analytical model introduced previously in the literature; and (iii)an iterative correction approach proposed here. The three correction methods are compared using simulated data for a range of RF flip angles and RF repetition times. The correction methods are also tested on experimental data obtained with dynamic nuclear polarization (DNP) using 4-oxo-TEMPO in H glassy matrices. It is demonstrated that the analytical and iterative corrections allow us to obtain accurate build-up times and steady-state polarizations (enhancements) for RF flip angles of up to 25 during the polarization build-up process within % error when compared to data acquired with small RF flip angles ( ). For polarization decay experiments, corrections are shown to be accurate for RF flip angles of up to 12. In conclusion, the proposed iterative correction allows us to compensate for the impact of RF pulses offering an accurate estimation of polarization levels, build-up and decay time constants in hyperpolarization experiments.

Modelling of T1 dispersion effects on fluid polarization in oil flow

In this article we use numerical simulations to study the effect of T1 dispersion on fluid polarization buildup in oil flow to characterize the sensitivity of both a conventional NMR concept (ROI located inside the polarization magnet) and a Earth's field NMR concept (ROI outside and downstream of the polarization magnet) to T1 dispersion of flowing samples. As a polarization field in both concepts we use a 90 cm long Halbach magnet. The T1 dispersion behavior of the oils is based on a set of crude oils that span a viscosity range of 0.7 cP up to 2·104 cP and T1 relaxation measurements for Larmor frequencies between 10 kHz and 20 MHz. Numerical simulations based on solving the Bloch-Torrey equation for the longitudinal magnetization component show that fluid polarization levels in a ROI of a Earth's field NMR system concept are much more strongly affected by T1 dispersion than in the conventional NMR system concept. As a result, we may conclude that the Earth's field NMR system design is less robust for measuring flowing samples that show strong T1 dispersion behavior. In comparison, the conventional NMR system design is relatively insensitive to the effect of T1 dispersion, as T1 dispersion effects were found to form a relatively small correction to the magnetization buildup. The conventional NMR system design consequently is the preferred implementation of a NMR system that operates on fluids with strong T1 dispersion behavior. We show that in the presence of T1 dispersion s = vT1(0)/Lm* may be used as a governing parameter for fluid polarization buildup, where T1(0) is the T1 relaxation time in the center of the polarization magnet, and we show how an modified analytical uniform field model can be used to describe fluid polarization for a uniform flow velocity distribution in the presence of T1 dispersion with an accuracy within 1% for the samples and field distribution considered in this study at industrially relevant flow velocities.

Serial Polarization Transfer by Combination of Cross-Relaxation and Rotational Resonance for Sensitivity-Enhanced Solid-State NMR.

Methods which induce site-specificity and sensitivity enhancement in solid-state magic-angle spinning NMR spectroscopy become more important for structural biology due to the increasing size of molecules under investigation. Recently, several strategies have been developed to increase site specificity and thus reduce signal overlap. Under dynamic nuclear polarization (DNP) for NMR signal enhancement, it is possible to use cross-relaxation transfer induced by select dynamic groups within the molecules which is exploited by SCREAM-DNP (Specific Cross Relaxation Enhancement by Active Motions under DNP). Here, we present an approach where we additionally reintroduce the homonuclear dipolar coupling with rotational resonance (R2) during SCREAM-DNP to further boost the selectivity of the experiment. Detailed analysis of the polarization buildup dynamics of 13C-methyl polarization source and 13C-carbonyl target in 2-13C-ethyl 1-13C-acetate provides information about the sought-after and spurious transfer pathways. We show that dipolar-recoupled transfer rates greatly exceed the DNP buildup dynamics in our model system, indicating that significantly larger distances can be selectively and efficiently hyperpolarized.

Theoretical Foundation of the Linear Relationship between the Midlatitude Eddy Heat Flux and Fall-to-Spring Polar Ozone Buildup

Abstract It has been demonstrated that there is a globally unified linear relationship between the interannual variations of the fall-to-spring polar ozone accumulation and the winter-mean poleward eddy heat flux on the 100 hPa pressure surface. The foundation of this relationship is investigated using time-slice experiments on a chemistry–climate model with two levels of ozone-depleting substances (ODSs). The features of the transport field are interpreted by decomposing the horizontal ozone flux caused by the residual circulation into contributing processes including the eddy heat flux with the aid of the transformed Eulerian-mean momentum equation followed by rearrangement of terms. The linear relationship between the interannual variations of the fall-to-spring ozone buildup integrated poleward and above a reference point Pref on a meridional plane and the poleward eddy heat flux during the corresponding period at Pref is realized for each hemisphere implying that the interhemispheric unification should be treated with caution. This relationship is interpreted using the fact that the interannual variation of poleward ozone transport in the upper stratosphere is captured well by the vertical convergence of the constituent-based Eliassen–Palm (EP) flux (), which is defined as the product of the constituent (ozone) mixing ratio and EP flux. The eddy momentum flux contributes to the meridional ozone transport in combination with the eddy heat flux in the form of the divergence of , although it is not responsible for realizing the linear relationship. The dependence of the linearity on the location of Pref and ODS levels is discussed.

Efficient SABRE-SHEATH Hyperpolarization of Potent Branched-Chain-Amino-Acid Metabolic Probe [1-13C]ketoisocaproate.

Efficient 13C hyperpolarization of ketoisocaproate is demonstrated in natural isotopic abundance and [1-13C]enriched forms via SABRE-SHEATH (Signal Amplification By Reversible Exchange in SHield Enables Alignment Transfer to Heteronuclei). Parahydrogen, as the source of nuclear spin order, and ketoisocaproate undergo simultaneous chemical exchange with an Ir-IMes-based hexacoordinate complex in CD3OD. SABRE-SHEATH enables spontaneous polarization transfer from parahydrogen-derived hydrides to the 13C nucleus of transiently bound ketoisocaproate. 13C polarization values of up to 18% are achieved at the 1-13C site in 1 min in the liquid state at 30 mM substrate concentration. The efficient polarization build-up becomes possible due to favorable relaxation dynamics. Specifically, the exponential build-up time constant (14.3 ± 0.6 s) is substantially lower than the corresponding polarization decay time constant (22.8 ± 1.2 s) at the optimum polarization transfer field (0.4 microtesla) and temperature (10 °C). The experiments with natural abundance ketoisocaproate revealed polarization level on the 13C-2 site of less than 1%-i.e., one order of magnitude lower than that of the 1-13C site-which is only partially due to more-efficient relaxation dynamics in sub-microtesla fields. We rationalize the overall much lower 13C-2 polarization efficiency in part by less favorable catalyst-binding dynamics of the C-2 site. Pilot SABRE experiments at pH 4.0 (acidified sample) versus pH 6.1 (unaltered sodium [1-13C]ketoisocaproate) reveal substantial modulation of SABRE-SHEATH processes by pH, warranting future systematic pH titration studies of ketoisocaproate, as well as other structurally similar ketocarboxylate motifs including pyruvate and alpha-ketoglutarate, with the overarching goal of maximizing 13C polarization levels in these potent molecular probes. Finally, we also report on the pilot post-mortem use of HP [1-13C]ketoisocaproate in a euthanized mouse, demonstrating that SABRE-hyperpolarized 13C contrast agents hold promise for future metabolic studies.

Parallel detection of chemical reactions in a microfluidic platform using hyperpolarized nuclear magnetic resonance.

The sensitivity of NMR may be enhanced by more than four orders of magnitude via dissolution dynamic nuclear polarization (dDNP), potentially allowing real-time, in situ analysis of chemical reactions. However, there has been no widespread use of the technique for this application and the major limitation has been the low experimental throughput caused by the time-consuming polarization build-up process at cryogenic temperatures and fast decay of the hyper-intense signal post dissolution. To overcome this limitation, we have developed a microfluidic device compatible with dDNP-MR spectroscopic imaging methods for detection of reactants and products in chemical reactions in which up to 8 reactions can be measured simultaneously using a single dDNP sample. Multiple MR spectroscopic data sets can be generated under the same exact conditions of hyperpolarized solute polarization, concentration, pH, and temperature. A proof-of-concept for the technology is demonstrated by identifying the reactants in the decarboxylation of pyruvate via hydrogen peroxide (e.g. 2-hydroperoxy-2-hydroxypropanoate, peroxymonocarbonate and CO2). dDNP-MR allows tracing of fast chemical reactions that would be barely detectable at thermal equilibrium by MR. We envisage that dDNP-MR spectroscopic imaging combined with microfluidics will provide a new high-throughput method for dDNP enhanced MR analysis of multiple components in chemical reactions and for non-destructive in situ metabolic analysis of hyperpolarized substrates in biological samples for laboratory and preclinical research.

Electroplated waveguides to enhance DNP and EPR spectra of silicon and diamond particles.

Electroplating the waveguide of a 7 T polarizer in a simple innovative way increased microwave power delivered to the sample by 3.1 dB. Silicon particles, while interesting for hyperpolarized MRI applications, are challenging to polarize due to inefficient microwave multipliers at the electron Larmor frequency at high magnetic fields and fast electronic relaxation times. Improving microwave transmission directly translates to more efficient EPR excitation at high-field, low-temperature conditions and promises faster and higher Si polarization buildup through dynamic nuclear polarization (DNP).

Rapid 13C Hyperpolarization of the TCA Cycle Intermediate α-Ketoglutarate via SABRE-SHEATH.

α-Ketoglutarate is a key biomolecule involved in a number of metabolic pathways─most notably the TCA cycle. Abnormal α-ketoglutarate metabolism has also been linked with cancer. Here, isotopic labeling was employed to synthesize [1-13C,5-12C,D4]α-ketoglutarate with the future goal of utilizing its [1-13C]-hyperpolarized state for real-time metabolic imaging of α-ketoglutarate analytes and its downstream metabolites in vivo. The signal amplification by reversible exchange in shield enables alignment transfer to heteronuclei (SABRE-SHEATH) hyperpolarization technique was used to create 9.7% [1-13C] polarization in 1 minute in this isotopologue. The efficient 13C hyperpolarization, which utilizes parahydrogen as the source of nuclear spin order, is also supported by favorable relaxation dynamics at 0.4 μT field (the optimal polarization transfer field): the exponential 13C polarization buildup constant Tb is 11.0 ± 0.4 s whereas the 13C polarization decay constant T1 is 18.5 ± 0.7 s. An even higher 13C polarization value of 17.3% was achieved using natural-abundance α-ketoglutarate disodium salt, with overall similar relaxation dynamics at 0.4 μT field, indicating that substrate deuteration leads only to a slight increase (∼1.2-fold) in the relaxation rates for 13C nuclei separated by three chemical bonds. Instead, the gain in polarization (natural abundance versus [1-13C]-labeled) is rationalized through the smaller heat capacity of the "spin bath" comprising available 13C spins that must be hyperpolarized by the same number of parahydrogen present in each sample, in line with previous 15N SABRE-SHEATH studies. Remarkably, the C-2 carbon was not hyperpolarized in both α-ketoglutarate isotopologues studied; this observation is in sharp contrast with previously reported SABRE-SHEATH pyruvate studies, indicating that the catalyst-binding dynamics of C-2 in α-ketoglutarate differ from that in pyruvate. We also demonstrate that 13C spectroscopic characterization of α-ketoglutarate and pyruvate analytes can be performed at natural 13C abundance with an estimated detection limit of 80 micromolar concentration × *%P13C. All in all, the fundamental studies reported here enable a wide range of research communities with a new hyperpolarized contrast agent potentially useful for metabolic imaging of brain function, cancer, and other metabolically challenging diseases.

Multiaxial fields improve SABRE efficiency by preserving hydride order

Signal Amplification By Reversible Exchange (SABRE) and the heteronuclear variant, X-SABRE, increase the sensitivity of magnetic resonance techniques using order derived from reversible binding of para-hydrogen. One current limitation of SABRE is suboptimal polarization transfer over the lifetime of the complex. Here, we demonstrate a multiaxial low-field pulse sequence which allows optimal polarization build-up during a low-field “evolution” pulse, followed by a high-field “mixing” pulse which permits proton decoupling along an orthogonal axis. This preserves the singlet character of the hydrides while allowing exchange to replenish the ligands on the iridium catalyst. This strategy leads to a 2.5-fold improvement over continuous field SABRE SHEATH experimentally which was confirmed with numerical simulation.

Temperature-related effects in the polarization of atoms in a magnetized plasma as a promising feature towards high He3 nuclear polarization

We report on further investigation of nuclear hyperpolarization of $^{3}\mathrm{He}$ in magnetized plasma at a magnetic field of 3.66 T and at different experimental conditions in a dual cell of relatively large volume, compared to those reported in the original polarization of atoms in a magnetized plasma (PAMP) paper by Maul et al. [Phys. Rev. A 98, 063405 (2018)]. It was found that steady-state nuclear polarizations obtained by this method strongly increase with temperature and rf gas discharge power. We managed to reach almost 8% at the highest possible temperature in our setup which is to date the highest polarization obtained by this method at 10 mbar. It was also shown that atomic oxygen in plasma, considered as an impurity, could be a good probe of plasma parameters relevant for the PAMP process, either in the temperature or the metastable $^{3}\mathrm{He}$ density. The polarization buildup rates with the cell temperature stabilized near room temperature are found to be of the order of 1 ${\mathrm{s}}^{\ensuremath{-}1}$, which is by two orders of magnitude faster than was reported in the original PAMP paper for the same filling pressure. These observations promise a further optimization of experimental conditions towards strong and fast hyperpolarization by this method.

Performance and reproducibility of 13C and 15N hyperpolarization using a cryogen-free DNP polarizer

The setup, operational procedures and performance of a cryogen-free device for producing hyperpolarized contrast agents using dissolution dynamic nuclear polarization (dDNP) in a preclinical imaging center is described. The polarization was optimized using the solid-state, DNP-enhanced NMR signal to calibrate the sample position, microwave and NMR frequency and power and flip angle. The polarization of a standard formulation to yield ~ 4 mL, 60 mM 1-13C-pyruvic acid in an aqueous solution was quantified in five experiments to P(13C) = (38 ± 6) % (19 ± 1) s after dissolution. The mono-exponential time constant of the build-up of the solid-state polarization was quantified to (1032 ± 22) s. We achieved a duty cycle of 1.5 h that includes sample loading, monitoring the polarization build-up, dissolution and preparation for the next run. After injection of the contrast agent in vivo, pyruvate, pyruvate hydrate, lactate, and alanine were observed, by measuring metabolite maps. Based on this work sequence, hyperpolarized 15N urea was obtained (P(15N) = (5.6 ± 0.8) % (30 ± 3) s after dissolution).

Physical link of the polar field buildup with the Waldmeier effect broadens the scope of early solar cycle prediction: Cycle 25 is likely to be slightly stronger than Cycle 24

ABSTRACT Prediction of the solar cycle is challenging but essential because it drives space weather. Several predictions with varying amplitudes of the ongoing Cycle 25 have been made. We show that an aspect of the Waldmeier effect (WE2), i.e. a strong positive correlation between the rise rate and the amplitude of the cycle, has a physical link with the buildup of the previous cycle’s polar field after its reversal. We find that the rise rate of the polar field is highly correlated with the rise rate and the amplitude of the next solar cycle. Thus, the prediction of the amplitude of the solar cycle can be made just a few years after the reversal of the previous cycle’s polar field, thereby extending the scope of the solar cycle prediction to much earlier than the usual time. Our prediction of Cycle 25 based on the rise rate of the previous polar field is 137 ± 23, which is quite close to the prediction 138 ± 26 based on the WE2 computed from the available 2 yr sunspot data of the ongoing cycle.

Polarization Transfer from Optically Pumped Ensembles of N- V Centers to Multinuclear Spin Baths

Nitrogen-vacancy (N-$V$) diamonds have attracted keen interest for nanoscale sensing and spin manipulation. In particular, the nonequilibrium electron spin polarization after optical excitation of single N-$V$ centers has successfully been transferred to nuclear spin baths in the surrounding of defects. However, these experiments need to be extended to N-$V$ ensembles that have promising practical applications in the hyperpolarization of bulk sample volumes for NMR signal enhancement. Here, we use a dense, shallow ensemble of N-$V$ centers to demonstrate polarization transfer to nuclear spins in a well-defined composite diamond sample system. This allows us to address three different types of nuclear spins in different positions with respect to the N-$V$ polarization source: from the close proximity of ${}^{13}\mathrm{C}$ inside the diamond lattice to the self-assembled molecular system consisting of ${}^{1}\mathrm{H}$ and ${}^{19}\mathrm{F}$ spins outside the diamond and over multiple interfaces. We show that ensemble N-$V$ experiments face problems different from single N-$V$ experiments. In particular, using spinlock pulses, the inhomogeneously broadened electron spin resonance line of the N-$V$ ensemble limits the minimal resonance linewidth with which the transfer protocol can occur. Furthermore, we compare the N-$V$ spin-polarization losses and polarization transfer rates to the different nuclear baths and discuss the role of spin diffusion as detrimentally affecting the direct observation of nuclear polarization buildup within the detection volume of nanoscale N-$V$-NMR experiments.