Nuclear Magnetic Resonance Shifts Research Articles

NMR shift and relaxation measurements in pulsed high-field magnets up to 58 T

Nuclear magnetic resonance (NMR) experiments at fields up to 58T in pulsed magnets at the Dresden High Magnetic Field Laboratory are reported. The challenge to resolve NMR shifts in these time-dependent fields is addressed for the first time, and it is shown that this can indeed be accomplished with high precision with an internal reference. As a result, signal averaging is possible during a single magnetic field pulse, but also for multiple pulses. Thus, even very weak signals can in principle be recorded and their shifts can be determined. In a second set of experiments, the measurement of nuclear relaxation is investigated. Using adiabatic inversion with the inherent time dependence of the magnetic field and small-angle inspection, it is shown that relaxation measurements are possible, as well. The shift experiments were performed with 27Al NMR on a mixture of aluminum metal and a Linde type A zeolite. For the relaxation studies, 27Al NMR and 69Ga NMR on the metals aluminum and gallium were preformed, respectively.

Anvil cell gasket design for high pressure nuclear magnetic resonance experiments beyond 30 GPa

Nuclear magnetic resonance (NMR) experiments are reported at up to 30.5 GPa of pressure using radiofrequency (RF) micro-coils with anvil cell designs. These are the highest pressures ever reported with NMR, and are made possible through an improved gasket design based on nano-crystalline powders embedded in epoxy resin. Cubic boron-nitride (c-BN), corundum (α-Al2O3), or diamond based composites have been tested, also in NMR experiments. These composite gaskets lose about 1/2 of their initial height up to 30.5 GPa, allowing for larger sample quantities and preventing damages to the RF micro-coils compared to precipitation hardened CuBe gaskets. It is shown that NMR shift and resolution are less affected by the composite gaskets as compared to the more magnetic CuBe. The sensitivity can be as high as at normal pressure. The new, inexpensive, and simple to engineer gaskets are thus superior for NMR experiments at high pressures.

Phase transition of carbonate solvent mixture solutions at low temperatures

The phase transition of carbonate solvent mixture solutions consisting of ethylene carbonate (EC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), and LiPF6 salt have been studied for improving the low temperature performance of lithium-ion batteries.The Li ion conductivity at 25 °C was maximum at x = 0.3 in a series of 1 M LiPF6 mixed carbonate solvents compositions consisting of ECxDMC0.5−0.5xEMC0.5−0.5x (x = 0 to 0.6), while the maximum tended to shift to x = 0.2 as the temperature lowered. The differential scanning calorimetry results showed that the freezing temperature depressions of EC in the 1 M LiPF6 solution were larger than those of the DMC or EMC. The chemical shift of 7Li nuclear magnetic resonance changed from a constant to increasing at around x = 0.3, which could be reasonably understood by focusing on the change in solvation energy calculated using Born equation. However, in the region of a high EC concentration of over x = 0.3 (EC/LiPF6 > 4) in the 1 M LiPF6 solution, the free EC from the solvation to the lithium ions seems to reduce the freezing temperature depression of the EC, and thus, decreases the ionic conductivity of the solution at low temperatures, due to the EC freezing.

Synthesis, Structural Characterization, and Chiroptical Studies of Bidentate Salen-Type Lanthanide (III) Complexes.

The salen-type ligand prepared with (R,R) diphenylethan-1,2-diamine and salicylaldehyde provides stable and inert complexes KLnL2 upon simple reaction with lanthanide halides or pseudohalides LnX3 (Ln = Tb(3+) -Lu(3+) ; X = Cl(-) or TfO(-) ) of its potassium salt. All the complexes were completely characterized through nuclear magnetic resonance (NMR), electronic circular dichroism (ECD) in the UV and some (Er(3+) , Tm(3+) , Yb(3+) ) also with Near-IR ECD (NIR-ECD) and luminescence (Tb(3+) , Tm(3+) ). Careful analysis of the NMR shifts demonstrated that the complexes are isostructural in solution and afforded an accurate geometry. This was further confirmed by means of Density Functional Theory (DFT) optimization of the Lu(3+) complex, and by comparing the ligand-centered experimental and time-dependent TD-DFT computed UV-ECD spectra. As final validation, we used the NIR-ECD spectrum of the Yb(3+) derivative calculated by means of Richardson's equations. The excellent match between calculated and experimental ECD spectra confirm the quality of the NMR structure.

Enhanced superconducting transition temperature in hyper-interlayer-expanded FeSe despite the suppressed electronic nematic order and spin fluctuations

The superconducting critical temperature, $T_{\rm c}$, of FeSe can be dramatically enhanced by intercalation of a molecular spacer layer. Here we report on a $^{77}$Se, $^7$Li and $^1$H nuclear magnetic resonance (NMR) study of the powdered hyper-interlayer-expanded Li$_{x}($C$_2$H$_8$N$_2$)$_y$Fe$_{2-z}$Se$_2$ with a nearly optimal $T_{\rm c}=45$~K. The absence of any shift in the $^7$Li and $^1$H NMR spectra indicates a complete decoupling of interlayer units from the conduction electrons in FeSe layers, whereas nearly temperature-independent $^7$Li and $^1$H spin-lattice relaxation rates are consistent with the non-negligible concentration of Fe impurities present in the insulating interlayer space. On the other hand, strong temperature dependence of $^{77}$Se NMR shift and spin-lattice relaxation rate, $1/^{77}T_1$, is attributed to the hole-like bands close to the Fermi energy. $1/^{77}T_1$ shows no additional anisotropy that would account for the onset of electronic nematic order down to $T_{\rm c}$. Similarly, no enhancement in $1/^{77}T_1$ due to the spin fluctuations could be found in the normal state. Yet, a characteristic power-law dependence $1/^{77}T_1\propto T^{4.5}$ still comply with the Cooper pairing mediated by spin fluctuations.

(1)H NMR spectra of alcohols in hydrogen bonding solvents: DFT/GIAO calculations of chemical shifts.

Proton nuclear magnetic resonance (NMR) shifts of aliphatic alcohols in hydrogen bonding solvents have been computed on the basis of density functional theory by applying the gauge-including atomic orbital method to geometry-optimized alcohol/solvent complexes. The OH proton shifts and hydrogen bond distances for methanol or ethanol complexed with pyridine depend very much on the functional employed and very little on the basis set, provided it is sufficiently large to give the correct quasi-linear hydrogen bond geometry. The CH proton shifts are insensitive to both the functional and the basis set. NMR shifts for all protons in several alcohol/pyridine complexes are calculated at the Perdew, Burke and Ernzerhof PBE0/cc-pVTZ//PBE0/6-311 + G(d,p) level in the gas phase. The results correlate with the shifts for the pyridine-complexed alcohols, determined by analysing data from the NMR titration of alcohols against pyridine. More pragmatically, computed shifts for a wider range of alcohols correlate with experimental shifts in neat pyridine. Shifts for alcohols in dimethylsulfoxide, based on the corresponding complexes in the gas phase, correlate well with the experimental values, but the overall root mean square difference is high (0.23 ppm), shifts for the OH, CHOH and other CH protons being systematically overestimated, by averages of 0.42, 0.21 and 0.06 ppm, respectively. If the computed shifts are corrected accordingly, a very good correlation is obtained with a gradient of 1.00 ± 0.01, an intercept of 0.00 ± 0.02 ppm and a root mean square difference of 0.09 ppm. This is a modest improvement on the result of applying the CHARGE programme to a slightly different set of alcohols. Some alcohol complexes with acetone and acetonitrile were investigated both in the gas phase and in a continuum of the relevant solvent.

Relativistic Effects in NMR of New Prospective Water-Soluble Ligands SeP(CH2OH)3 and H[Se2P(CH2OH)2

We present the synthesis of new phosphine selenide SeP(CH2OH)3 and diselenophosphinate H[Se2P(CH2OH)2] and their characterization with nuclear magnetic resonance (NMR) spectroscopy and quantum chemistry methods. DFT calculations show large relativistic spin–orbit effects in NMR shielding of phosphorus nuclei. We discuss the impact of Se lone pairs and electrons of P–Se and P–C bonds on the 31P NMR shift and, especially, its relativistic part. The description of P–Se bonds and characterization of electron lone pairs on Se atoms are carried out with the help of natural localized molecular orbitals analysis and topological analysis of electron localization function.

Structure elucidation of the designer drug N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide and the relevance of predicted (13) C NMR shifts - a case study.

The detailed structure elucidation process of the new cannabimimetic designer drug, N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, with a highly substituted pyrazole skeleton, using nuclear magnetic resonance (NMR) spectroscopic and mass spectrometric (MS) techniques is described. After a first analysis of the NMR spectra and comparison with 48 possible pyrazole and imidazole structures, a subset of six positional isomeric pyrazoles and six imidazoles remained conceivable. Four substituents of the heterocyclic skeleton were identified: a proton bound to a pyrazole ring carbon atom; a 5-fluoropentyl group; a 4-fluorophenyl substituent; and a carbamoyl group, which is N-substituted with a methyl residue carrying a tert.-butyl and a carbamoyl substituent. The 5-fluoropentyl residue is situated at the nitrogen ring atom. Additional NMR experiments like the (1) H,(13) C HMBC were performed, but due to the small number of signals based on long-range couplings, the comparison of predicted and observed (13) C chemical shifts became necessary. The open access Internet shift prediction programs NMRDB, NMRSHIFTDB2, and CSEARCH were employed for the prediction of (13) C shift values which allowed an efficient and unambiguous structure determination. For the identified N-(1-amino-3,3-dimethyl-1-oxobutan-2-yl)-1-(5-fluoropentyl)-3-(4-fluorophenyl)-pyrazole-5-carboxamide, the best agreement between predicted (13) C shifts and the observed chemical shifts and long-range couplings for the pyrazole ring carbon atoms, with a standard error of about 2 ppm, was found with each of the predictions. For the comparison of measured and predicted chemical shifts model compounds with simple substituents proved helpful. The identified compound is a homologue of AZ-037 which is offered by Internet suppliers. Copyright © 2015 John Wiley & Sons, Ltd.

Simple Resolution of Enantiomeric NMR Signals of α-Amino Acids by Using Samarium(III) Nitrate With L-Tartarate.

Readily available L-tartaric acid, which is a bidentate ligand with two chiral centers forming a seven-membered chelate ring, was applied to the chiral ligand for the chiral nuclear magnetic resonance (NMR) shift reagent of samarium(III) formed in situ. This simple method does not cause serious signal broadening in the high magnetic field. Enantiomeric (13)C and (1)H NMR signals and enantiotopic (1)H NMR signals of α-amino acids were successfully resolved at pH 8.0 and the 1:3 molar ratio of Sm(NO3)3:L-tartaric acid. It is elucidated that the enantiomeric signal resolution is attributed to the anisotropic magnetic environment for the enantiomers induced by the chiral L-tartarato samarium(III) complex rather than differences in stability of the diastereomeric substrate adducts. The present (13)C NMR signal resolution was also effective for the practical simultaneous analysis of plural kinds of DL-amino acids.

Hyperfine coupling and spin polarization in the bulk of the topological insulatorBi2Se3

Nuclear magnetic resonance (NMR) and transport measurements have been performed at high magnetic fields and low temperatures in a series of $n$-type Bi$_{2}$Se$_{3}$ crystals. In low density samples, a complete spin polarization of the electronic system is achieved, as observed from the saturation of the isotropic component of the $^{209}$Bi NMR shift above a certain magnetic field. The corresponding spin splitting, defined in the phenomenological approach of a 3D electron gas with a large (spin-orbit-induced) effective $g$-factor, scales as expected with the Fermi energy independently determined by simultaneous transport measurements. Both the effective electronic $g$-factor and the "contact" hyperfine coupling constant are precisely determined. The magnitude of this latter reveals a non negligible $s$-character of the electronic wave function at the bottom of the conduction band. Our results show that the bulk electronic spin polarization can be directly probed via NMR and pave the way for future NMR investigations of the electronic states in Bi-based topological insulators.

11B pulsed nuclear magnetic resonance study of HoB4

11B pulsed nuclear magnetic resonance (NMR) measurements were performed on a single crystal of HoB4 to investigate disorder-induced effects on the 4f spin structures and dynamics. The 11B NMR spectrum, shift, linewidth, and spin-lattice and spin–spin relaxation rates (1/T1 and 1/T2, respectively) were measured down to 3.5 K at a field of 8 T perpendicular to the c-axis. Above the Né el temperature, TN = 5.7 K, the 11B NMR linewidth is very large and the shift is also large and with negative sign. In addition, both are strongly temperature-dependent and the absolute shift value and linewidth increase at lower temperatures. This fact confirms that the hyperfine field at the boron sites originates mainly from the Ho 4f spins, as this is also the case for the susceptibility. Below TN, the 11B NMR spectrum displays a single, broad and featureless shape with an extremely large linewidth. This behavior is an unexpected result compared with typical NMR spectra in the magnetically ordered state for single crystal specimens, and is significantly different to that of other RB4 substances. Considering frustration and disorder effects on the static and dynamic NMR data, we conclude that this behavior originates from the magnetic frustration and quadrupole moment disorder effects on the NMR static data, since the Ho ions form a Shastry-Sutherland (SS)-type lattice in the ab plane. Above TN, both relaxation rates (1/T1 and 1/T2) are very large as a result of the rapid and random fluctuation of the Ho 4f moments, and they then increase toward the Né el transition. Below TN, both rates decrease significantly since the 4f spin fluctuations and dynamics are frozen as a result of the antiferromagnetic ordering.

Antiferromagnetism ofZn2VO(PO4)2and the dilution withTi4+

We report static and dynamic properties of the antiferromagnetic compound Zn$_{2}$(VO)(PO$_{4}$)$_{2}$, and the consequences of non-magnetic Ti$^{4+}$ doping at the V$^{4+}$ site. $^{31}$P nuclear magnetic resonance (NMR) spectra and spin-lattice relaxation rate ($1/T_1$) consistently show the formation of the long-range antiferromagnetic order below $T_N= 3.8-3.9$\,K. The critical exponent $\beta=0.33 \pm 0.02$ estimated from the temperature dependence of the sublattice magnetization measured by $^{31}$P NMR at 9.4\,MHz is consistent with universality classes of three-dimensional spin models. The isotropic and axial hyperfine couplings between the $^{31}$P nuclei and V$^{4+}$ spins are $A_{\rm hf}^{\rm iso} = (9221 \pm 100)$ Oe/$\mu_{\rm B}$ and $A_{\rm hf}^{\rm ax} = (1010 \pm 50)$ Oe/$\mu_{\rm B}$, respectively. Magnetic susceptibility data above 6.5\,K and heat capacity data above 4.5\,K are well described by quantum Monte-Carlo simulations for the Heisenberg model on the square lattice with $J\simeq 7.7$\,K. This value of $J$ is consistent with the values obtained from the NMR shift, $1/T_1$ and electron spin resonance (ESR) intensity analysis. Doping Zn$_2$VO(PO$_4)_2$ with non-magnetic Ti$^{4+}$ leads to a marginal increase in the $J$ value and the overall dilution of the spin lattice. In contrast to the recent \textit{ab initio} results, we find neither evidence for the monoclinic structural distortion nor signatures of the magnetic one-dimensionality for doped samples with up to 15\% of Ti$^{4+}$. The N\'eel temperature $T_{\rm N}$ decreases linearly with increasing the amount of the non-magnetic dopant.

Determination of absolute configuration in chiral solvents with nuclear magnetic resonance. A combined molecular dynamics/quantum chemical study.

Nuclear magnetic resonance (NMR) spectroscopy is omnipresent in chemical analysis. However, chirality of a molecule can only be detected indirectly by NMR, e.g., by monitoring its interaction with another chiral object. In the present study, we investigate the spectroscopic behavior of chiral molecules placed into a chiral solvent. In this case, the solvent-solute interaction is much weaker, but the application range of such NMR analysis is wider than for a specific chemical shift agent. Two alcohols and an amine were used as model systems, and differences in NMR chemical shifts dependent on the solute-solvent chirality combination were experimentally detected. Combined quantum mechanic/molecular mechanic (QM/MM) computations were applied to reveal the underlying solute-solvent interactions. NMR shielding was calculated using the density functional theory (DFT). While the experimental observations could not be reproduced quantitatively, the modeling provided a qualitative agreement and detailed insight into the essence of solvent-solute chiral interactions. The potentials of mean force (PMF) obtained using molecular dynamics (MD) and the weighted histogram analysis method (WHAM) indicate that the chiral interaction brings about differences in conformer ratios, which are to a large extent responsible for the NMR shifts. The MD results also predicted slight changes in the solvent structure, including the radial distribution function (RDF), to depend on the solvent/solute chirality combination. Apart from the conformer distribution, an effective average solvent electrostatic field was tested as another major factor contributing to the chiral NMR effect. The possibility to simulate spectral effects of chiral solvents from the first-principles opens up the way to NMR spectroscopic determination of the absolute configuration for a larger scale of compounds, including those not forming specific complexes.

Relationship between gas chromatographic retention indices and chemical shifts in the 13C NMR spectra of structural isomers of compounds of tetracoordinated phosphorus

A method for determining the gas chromatographic retention indices of structural isomers of compounds of tetracoordinated phosphorus, based on the correlation between chemical shifts in 13C nuclear magnetic resonance (NMR) spectra and the retention indices of the structural isomers, and on the theory of intermolecular interactions, is proposed. The capabilities of the method are demonstrated for structural isomers of O-alkylmethylfluorophosphonates, which are typical representatives of compounds from the class of tetracoordinated phosphonates. The results from using the correlation approach are compared to experimental data.

NMR investigation of atomic and electronic structures of half-Heusler topologically nontrivial semimetals

209Bi nuclear magnetic resonance (NMR) spectroscopy was employed to probe potential spin-orbit effects on orbital diamagnetism in YPtBi and YPdBi crystals. The observed opposite sign and temperature dependent magnitude of 209Bi NMR shifts of both crystals reveal experimental signatures of enhanced orbital diamagnetism induced by spin-orbit interactions. This investigation indicates that NMR isotropic shifts might be beneficial in search of interesting spin-electronic phases among a vast number of topological nontrivial half-Heusler semimetals.

Anomalous local spin susceptibilities in noncentrosymmetricLa2C3superconductor

We report on $^{139}\mathrm{La}$ and $^{13}\mathrm{C}$ nuclear magnetic resonance (NMR) study of noncentrosymmetric superconductor ${\mathrm{La}}_{2}{\mathrm{C}}_{3}$ with superconducting critical temperature ${T}_{\mathrm{c}}=11.8$ K. In the normal state $^{139}\mathrm{La}$ NMR spectra show a characteristic quadrupole polycrystalline broadening yielding a quadrupole frequency ${\ensuremath{\nu}}_{\mathrm{Q}}\phantom{\rule{0.16em}{0ex}}=\phantom{\rule{0.16em}{0ex}}3.1$ MHz and a very large shift of $\ensuremath{\sim}3000$ ppm. A significant part of this shift arises from the Van Vleck-like susceptibility as a result of a sizable spin-orbit coupling. In the superconducting phase ${\mathrm{La}}_{2}{\mathrm{C}}_{3}$ shows abnormal behavior that dramatically deviates from the conventional $s$-wave superconductors. Namely, (i) $^{139}\mathrm{La}$ and $^{13}\mathrm{C}$ NMR shifts in the superconducting state do not change from their normal-state values, and (ii) the $^{139}\mathrm{La}$ spin-lattice relaxation rate is strongly enhanced below ${T}_{\mathrm{c}}$. Such unconventional response in the local static and dynamic spin susceptibilities is discussed in terms of possible mixture of spin-singlet and spin-triplet Cooper pairs, which is promoted by the asymmetric spin-orbit coupling in the system without the center of inversion.

1H NMR spectra of alcohols and diols in chloroform: DFT/GIAO calculation of chemical shifts.

Proton nuclear magnetic resonance (NMR) shifts of aliphatic alcohols in chloroform have been computed on the basis of density functional theory, the solvent being included by the integral-equation-formalism polarisable continuum model of Gaussian 09. Relative energies of all conformers are calculated at the Perdew, Burke and Ernzerhof (PBE)0/6-311+G(d,p) level, and NMR shifts by the gauge-including atomic orbital method with the PBE0/6-311+G(d,p) geometry and the cc-pVTZ basis set. The 208 computed CH proton NMR shifts for 34 alcohols correlate very well with the experimental values, with a gradient of 1.00 ± 0.01 and intercept close to zero; the overall root mean square difference (RMSD) is 0.08 ppm. Shifts for CH protons of diols in chloroform are well correlated with the theoretical values for (isotropic) benzene, with similar gradient and intercept (1.02 ± 0.01, -0.13 ppm), but the overall RMSD is slightly higher, 0.12 ppm. This approach generally gives slightly better results than the CHARGE model of Abraham et al. The shifts of unsaturated alcohols in benzene have been re-examined with Gaussian 09, but the overall fit for CH protons is not improved, and OH proton shifts are worse. Shifts of vinyl protons in alkenols are systematically overestimated, and the correlation of computed shifts against the experimental data for unsaturated alcohols follows a quadratic equation. Splitting the 20 compounds studied into two sets, and applying empirical scaling based on the quadratic for the first set to the second set, gives an RMSD of 0.10 ppm. A multi-standard approach gives a similar result.

Solution structure of telomere binding domain of AtTRB2 derived from Arabidopsis thaliana

Telomere homeostasis is regulated by telomere-associated proteins, and the Myb domain is well conserved for telomere binding. AtTRB2 is a member of the SMH (Single-Myb-Histone)-like family in Arabidopsis thaliana, having an N-terminal Myb domain, which is responsible for DNA binding. The Myb domain of AtTRB2 contains three α-helices and loops for DNA binding, which is unusual given that other plant telomere-binding proteins have an additional fourth helix that is essential for DNA binding. To understand the structural role for telomeric DNA binding of AtTRB2, we determined the solution structure of the Myb domain of AtTRB2 (AtTRB21–64) using nuclear magnetic resonance (NMR) spectroscopy. In addition, the inter-molecular interaction between AtTRB21–64 and telomeric DNA has been characterized by the electrophoretic mobility shift assay (EMSA) and NMR titration analyses for both plant (TTTAGGG)n and human (TTAGGG)n telomere sequences. Data revealed that Trp28, Arg29, and Val47 residues located in Helix 2 and Helix 3 are crucial for DNA binding, which are well conserved among other plant telomere binding proteins. We concluded that although AtTRB2 is devoid of the additional fourth helix in the Myb-extension domain, it is able to bind to plant telomeric repeat sequences as well as human telomeric repeat sequences.

Crystallographic fragment screening: challenges, opportunities, lessons learned

Fragment-based approaches are now routinely applied for lead development in pharmaceutical drug research. Usually, a small but well selected library of low molecular weight compounds is pre-screened by biochemical or biophysical methods such as surface plasmon resonance (SPR), nuclear magnetic resonance (NMR) or thermal shift assay; often followed for promising hit candidates by X-ray crystallography. We designed a small fragment library consisting of 364 compounds that is not strictly compliant to the otherwise often followed Astex rule of three for fragment library composition.[1] Thereafter, our library was validated on the pepsin-like aspartyl protease endothiapepsin, which serves as a model system for proteins that are involved in serious diseases such as malaria (plasmepsins), hypertension (renin) and Alzheimer's disease (ß-secretase) and therefore, is a valid target for further drug development. Due to the small size of fragments, they frequently exhibit only low affinity to the applied target protein and thus are often hard to detect in any screening approach, reflected in little overlap between different screening methods. After initial screening, we decided to validate the entire library by X-ray crystallography, which requires a steady supply of crystals, reproducible soaking conditions and a reliable setup at a synchrotron source, such as HZB BESSY II BL14.1 [2], preferably with some automation in initial data processing and refinement. A total hit rate greater than 10% was obtained, which will be compared to results from other screening methods. The resulting crystal structures will be discussed and provide an ideal basis for further lead development.

Li2ZnV3O8: a vanadium-based geometrically frustrated spinel system

We report the synthesis and characterization of Li2ZnV3O8, which is a new Zn-doped LiV2O4 system containing only tetravalent vanadium. A Curie–Weiss susceptibility with a Curie–Weiss temperature of θCW ≈ −214 K suggests the presence of strong antiferromagnetic correlations in this system. We have observed a splitting between the zero-field cooled (ZFC) and field cooled (FC) susceptibility curves below 6 K. A peak is present in the ZFC curve around 3.5 K, suggestive of spin-freezing. Similarly, a broad hump is also seen in the inferred magnetic heat capacity around 9 K. The consequent entropy change is only about 8% of the value expected for an ordered S = 1/2 system. This reduction indicates the continued presence of large disorder in the system in spite of the large θCW, which might result from strong geometric frustration in the system. We did not find any temperature T dependence in our 7Li nuclear magnetic resonance shift down to 6 K (an abrupt change in the shift does take place below 6 K), though considerable T-dependence has been found in the literature for LiV2O4—undoped or with other Zn/Ti contents. Consistent with the above observation, the 7Li nuclear spin-lattice relaxation rate 1/T1 is relatively small and nearly T-independent, except for a small increase close to the freezing temperature which, once again, is small compared to undoped or 10% Zn or 20% Ti-doped LiV2O4.