Paramagnetic Shifts Research Articles

Cluster-size dependent internal dynamics and magnetic anisotropy of Ho ions in HoM2N@C80and Ho2MN@C80families (M = Sc, Lu, Y)

The paramagnetic NMR study of HoM2N@C80-Ih and Ho2MN@C80-Ih nitride cluster fullerenes (M = Sc, Lu, Y) reveals strong dependence of Ho-induced paramagnetic shifts (δ(para)) in (13)C NMR spectra on the size of the diamagnetic metal in the cluster. In particular, the δ(para) value in HoY2N@C80 is almost doubled in comparison to that in HoSc2N@C80. X-ray magnetic circular dichroism studies show that all Ho-nitride cluster fullerenes have the same magnetic ground state of Ho(3+). Point-charge ligand-field splitting calculations show that the increase of the M(3+) radius in going from Sc to Y results in a considerable increase of the energy splitting between different Jz states. This leads to a 19% higher magnetic anisotropy of Ho(3+) in HoY2N@C80 than in HoSc2N@C80 at 300 K. Variations of the molecular geometry and cluster dynamics with the size of the cluster are found to have even greater influence on δ(para) values. This work shows that the magnetic properties of the species confined inside the fullerene cages can be tuned using the geometrical factors such as the cluster and the cage size.

Local Structure and Spin State of Cobalt Ion at Defect in Lithium Overstoichiometric LiCoO2 As Studied by 6/7Li Solid-State NMR Spectroscopy

Lithium overstoichiometric LixCoO2 (x > 1) with few phase transitions is promising as a positive electrode material for lithium ion batteries; however, the detailed lithium local structures around excess Li ions remain unknown and need to be elucidated. It has been postulated that the excess Li ion occupies the Co site, and the resulting charge deficit is compensated for by oxygen vacancies and the valence of Co. Two spin states have been invoked for the Co ion; one is Co3+ taking an intermediate spin state (S = 1) and the other is low spin Co2+ (S = 1/2). The paramagnetic shift caused by the Co spin is appreciable by 6/7Li nuclear magnetic resonance (NMR) in solids using magic-angle spinning (MAS), and we show that there are five “major” minor signals at ca. −16, −6, 3, 185, and 1100 ppm with the intensity ratio of 2:4:4:2:0.5–1.0, in addition to the major signal at 0 ppm. Analysis of temperature-dependent 7Li shifts and also 6Li T1 experiments confirm that the observed shifts for these minor peaks are ascribed to the paramagnetic interaction. To examine distance proximities among these lithium ions at the minor sites, we apply three 7Li–7Li two-dimensional (2D) correlation experiments and show that the three minor lithium atoms, whose shifts are 3, −6, and −16 ppm, exist in the same Li layer. Further, from rotational-resonance recoupling experiment, it is indicated that the lithium appearing at −16 ppm is closest to that at ca. 185 ppm. Based on these results, we show that a defect structure assuming low spin Co2+ which is not associated with the oxygen vacancy is consistent with the NMR results. This leads us to invoke Li insertion at an interstitial site, which has been negated, for the position of the excess Li atom.

Entrapment of a neutral Tm(III)‐based complex with two inner‐sphere coordinated water molecules into PEG‐stabilized vesicles: towards an alternative strategy to develop high‐performance LipoCEST contrast agents for MR imaging

Chemical exchange saturation transfer (CEST) probes issued from the encapsulation of a water proton paramagnetic shift reagent into the inner aqueous volume of lipid vesicles provide an emerging class of frequency-selective contrast agents with huge potential in the field of molecular magnetic resonance imaging (MRI). This work deals with the generation of such LipoCEST agents properly designed to optimize, under isotonic conditions, the chemical shift offset of the intra-liposomal water protons as well as the number of exchangeable protons under reasonably low radiofrequency (RF) fields of saturation. The strategy lies in the loading of poly(ethylene glycol)-stabilized nanosized liposomes with uncharged lanthanide chelates, binding more than one water molecule in the first hydration sphere, exemplified here by [Tm(III)-DO3A (H2 O)2 ] complex. The key properties of the probes are demonstrated by complementary NMR investigations. The residence lifetime of the water molecules coordinated to the lanthanide center was outstandingly short (9.5 ± 0.2 ns from (17) O NMR), and indeed relevant for effective LipoCEST responsiveness. The (1) H NMR CEST spectra (7.01 T magnetic field) prove that the theoretically expected optimal sensitivity can be approximated in the nanomolar concentration range, at reasonably low RF presaturation pulses (6.7-12 μT) and saturation frequency offsets of the intra-liposomal water protons beyond 10 ppm, making possible selective irradiation in biological environment. CEST-MRI images (7.01 T magnetic field and 10-12 μT RF pulse) explicitly confirm the interest of these newly conceived LipoCEST agents, indeed among the most efficient ones developed so far under isosmotic conditions.

Solid-state NMR strategies for the structural characterization of paramagnetic NO adducts of Frustrated Lewis Pairs (FLPs)

By N,N addition of NO to the norbonane annulated borane-phosphane Frustrated Lewis pair (FLP) 1 a five-membered heterocyclic persistent aminoxyl radical 2 and its diamagnetic hydroxylamine reduction product 3 are prepared, and the comprehensive multinuclear solid state NMR characterization (1H, 11B, 19F, 31P) of these FLP adducts is reported. Signal quantification experiments using a standard addition method reveal that the 11B and 31P NMR signals observed in 2 actually arise from molecular impurities of 3 embedded in the paramagnetic crystal. In contrast analogous quantification experiments reveal that the 1H and 19F MAS-NMR spectra originate from spin-carrying molecules. Peak assignments are based on DFT-calculated Mulliken spin densities, which lead to the surprising result that the largest paramagnetic shift affecting a proton NMR resonance in 2 originates from intermolecular interactions. For the 19F nuclei, experiments and calculations indicate that paramagnetic shift effects are very small. In this case, assignments are based on DFT chemical shift calculations carried out on diamagnetic 3 and 19F(11B) Rotational Echo Adiabatic Passage DOuble Resonance (REAPDOR) experiments. The set of experiments described here defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.

Magnetic Properties of Endohedral Metallofullerenes: Single-Molecular Magnetism and Anisotropy

Endohedral metallofullerenes (EMFs) encapsulating lanthanide ions (Ln) are of particular interest because of the specific magnetic properties resulting from the combination of the partially filled 4f shell of metal ions, their exchange interactions in endohedral clusters, and shielding role of the carbon cage, which protects endohedral spin states from the outer environment. Inhomogeneous environment of Ln ions inside clusterfullerenes induces magnetic anisotropy and results in a number of magnetic phenomena. In particular, Dy-based nitride clusterfullerenes are the first EMFs to exhibit single molecular magnet (SMM) behaviour.1 Furthermore, completely different SMM behaviour of DySc2N@C80, Dy2ScN@C80, and Dy3N@C80 molecules shows that exchange interactions between Ln ions in EMFs has strong influence on the magnetic properties.2 Results of the SQUID and XMCD studies of different EMFs at low temperatures will be discussed in this contribution. Whereas SQUID and XMCD are of particular use for the study of the low-temperature effects, magnetic properties of EMFs at room-temperature are conveniently addressed by paramagnetic NMR spectroscopy,3 since paramagnetic chemical shift is proportional to the anisotropy of magnetic susceptibility. New results on the NMR studies for a series of LnSc2N@C80molecules will be reported.1. R. Westerström, J. Dreiser, C. Piamonteze, M. Muntwiler, S. Weyeneth, H. Brune, S. Rusponi, F. Nolting, A. Popov, S. Yang, L. Dunsch and T. Greber, J. Am. Chem. Soc., 2012, 134, 9840-9843.2. R. Westerström, J. Dreiser, C. Piamonteze, M. Muntwiler, S. Weyeneth, K. Krämer, S.-X. Liu, S. Decurtins, A. Popov, S. Yang, L. Dunsch and T. Greber, arXiv:cond-mat/0604365v1, 2013, 1310.5040.3. Y. Zhang, A. A. Popov, S. Schiemenz and L. Dunsch, Chem.-Eur. J., 2012, 18, 9691-9698.

Single Crystal Nuclear Magnetic Resonance Studies of LiMnxFe1-XPO4

LiMPO4 are orthorhombic crystals, belonging to the olivine family and exhibit exceptionally high applicability for electrochemical energy storage in lithium-ion secondary batteries due to their charge storage capacity, chemical and thermal stability, and cost. Furthermore, mixed transition metal ion compounds Li(M,M’)PO4 are particularly promising cathode materials because the redox voltage increases as from Fe to Mn, Ni, Co 1and the mixed compounds can be tailored for specific applications.The aim of these studies is to better understand the key role played by the transition metals such as Fe, Mn and particularly their mixtures in determining the properties of these materials. Single crystal 7Li and 31P NMR studies are used to obtain precise information on the magnetic environments of the lithium ions and phosphate groups which may ultimately be correlated with processes and structural features that determine the electrochemical behavior of these olivine phosphates.By measurements of 7Li and 31P NMR frequencies, i.e. ν = B0∙σ∙Ι, where B0 is the applied field and Ι is the nuclear spin, with crystal orientation, it is possible to determine interaction tensor components {σij } giving rise to the lithium and phosphorus shifts. The series of the single crystals of LiMPO4 were prepared by a reciprocal salt flux growth technique, which allows the facile preparation of single crystals up to 1 cm across with well-developed facets at relatively low temperatures. Crystals for the NMR measurements present their natural faceting2.X-ray diffraction measurements were performed in order to identify the principal crystallographic axes [100], [010] and [001] of the samples. Subsequently the crystals were fixed to a rigid insert in the NMR probe, which was mounted onto a goniometer and inserted between the gap of a permanent magnet (B0=2.1T). The use of a relatively low field strength allowed for acquisition of the entire rotation pattern within the spectrometer bandwidth. Rotations were made with the goniometer shaft perpendicular to applied magnetic field, in this way it was possible to generate 24 spectra, one every 15o, for each crystallographic axis [100],[010] and [001].Previous studies3 showed that in the case of 31P, crystals exhibit large (paramagnetic) shifts on the order of 3000ppm, primarily due to the hyperfine interactions between the unpaired electron spins of the paramagnetic ion and the phosphorus nuclei.The 7Li resonances are also strongly affected by the paramagnetic susceptibility though not to the same extent as 31P. However in addition, there is a nuclear quadrupole interaction which splits the resonance and provides information concerning the electric field gradientIn addition to the endpoints (Fe and Mn analogues), we present an NMR analysis of the mixed transition metal ion compounds LiFexMn1-xPO4 , where x = 0.25, 0.5, and 0.75 in order to shed some light on the degree of cation disorder between the lithium, phosphorus, and transition metal sites that can result in substantial degradation of cathode performance particularly with regard to reduced rate capability.This research was supported by the U.S. Department of Energy

Elemental, isotopic, and structural changes in Tagish Lake insoluble organic matter produced by parent body processes

AbstractHere, we present the results of a multitechnique study of the bulk properties of insoluble organic material (IOM) from the Tagish Lake meteorite, including four lithologies that have undergone different degrees of aqueous alteration. The IOM C contents of all four lithologies are very uniform and comprise about half the bulk C and N contents of the lithologies. However, the bulk IOM elemental and isotopic compositions vary significantly. In particular, there is a correlated decrease in bulk IOM H/C ratios and δD values with increasing degree of alteration—the IOM in the least altered lithology is intermediate between CM and CR IOM, while that in the more altered lithologies resembles the very aromatic IOM in mildly metamorphosed CV and CO chondrites, and heated CMs. Nuclear magnetic resonance (NMR) spectroscopy, C X‐ray absorption near‐edge (XANES), and Fourier transform infrared (FTIR) spectroscopy confirm and quantitate this transformation from CR‐like, relatively aliphatic IOM functional group chemistry to a highly aromatic one. The transformation is almost certainly thermally driven, and probably occurred under hydrothermal conditions. The lack of a paramagnetic shift in 13C NMR spectra and 1s‐σ* exciton in the C‐XANES spectra, both typically seen in metamorphosed chondrites, shows that the temperatures were lower and/or the timescales were shorter than experienced by even the least metamorphosed type 3 chondrites. Two endmember models were considered to quantitatively account for the changes in IOM functional group chemistry, but the one in which the transformations involved quantitative conversion of aliphatic material to aromatic material was the more successful. It seems likely that similar processes were involved in producing the diversity of IOM compositions and functional group chemistries among CR, CM, and CI chondrites. If correct, CRs experienced the lowest temperatures, while CM and CI chondrites experienced similar more elevated temperatures. This ordering is inconsistent with alteration temperatures based on mineralogy and O isotopes.

Structural, magnetic, and superconducting properties of pulsed-laser-deposition-grownLa1.85Sr0.15CuO4/La2/3Ca1/3MnO3superlattices on (001)-orientedLaSrAlO4substrates

Epitaxial ${\mathrm{La}}_{1.85}{\mathrm{Sr}}_{0.15}{\mathrm{CuO}}_{4}/{\mathrm{La}}_{2/3}{\mathrm{Ca}}_{1/3}{\mathrm{MnO}}_{3}$ (LSCO/LCMO) superlattices on $(001)$-oriented ${\mathrm{LaSrAlO}}_{4}$ substrates have been grown with pulsed laser deposition technique. Their structural, magnetic, and superconducting properties have been determined with in situ reflection high-energy electron diffraction, x-ray diffraction, specular neutron reflectometry, scanning transmission electron microscopy, electric transport, and magnetization measurements. We find that despite the large mismatch between the in-plane lattice parameters of LSCO ($a=0.3779$ nm) and LCMO ($a=0.387$ nm) these superlattices can be grown epitaxially and with a high crystalline quality. While the first LSCO layer remains clamped to the ${\mathrm{LaSrAlO}}_{4}$ substrate, a sizable strain relaxation occurs already in the first LCMO layer. The following LSCO and LCMO layers adopt a nearly balanced state in which the tensile and compressive strain effects yield alternating in-plane lattice parameters with an almost constant average value. No major defects are observed in the LSCO layers, while a significant number of vertical antiphase boundaries are found in the LCMO layers. The LSCO layers remain superconducting with a relatively high superconducting onset temperature of ${T}_{c}^{\text{onset}}\ensuremath{\approx}36$ K. The macroscopic superconducting response is also evident in the magnetization data due to a weak diamagnetic signal below 10 K for $H$ $\ensuremath{\parallel}$ $ab$ and a sizable paramagnetic shift for $H$ $\ensuremath{\parallel}$ $c$ that can be explained in terms of a vortex-pinning-induced flux compression. The LCMO layers maintain a strongly ferromagnetic state with a Curie temperature of ${T}^{\text{Curie}}\ensuremath{\approx}190$ K and a large low-temperature saturation moment of about 3.5(1) ${\ensuremath{\mu}}_{B}$ per Mn ion. These results suggest that the LSCO/LCMO superlattices can be used to study the interaction between the antagonistic ferromagnetic and superconducting orders and, in combination with previous studies on ${\text{YBa}}_{2}{\text{Cu}}_{3}{\text{O}}_{7\ensuremath{-}x}/{\text{La}}_{2/3}{\text{Ca}}_{1/3}{\text{MnO}}_{3}$ superlattices, may allow one to identify the relevant mechanisms.

Artificial heme-proteins: determination of axial ligand orientations through paramagnetic NMR shifts

An empirical equation, describing the relationship between the porphyrin methyl hyperfine shifts and the position of the axial ligand(s), has been applied to an artificial heme-protein in order to obtain insight into the active site properties of heme-protein models.

Predicting paramagnetic 1H NMR chemical shifts and state-energy separations in spin-crossover host-guest systems.

The behaviour of metal-organic cages upon guest encapsulation can be difficult to elucidate in solution. Paramagnetic metal centres introduce additional dispersion of signals that is useful for characterisation of host-guest complexes in solution using nuclear magnetic resonance (NMR). However, paramagnetic centres also complicate spectral assignment due to line broadening, signal integration error, and large changes in chemical shifts, which can be difficult to assign even for known compounds. Quantum chemical predictions can provide information that greatly facilitates the assignment of NMR signals and identification of species present. Here we explore how the prediction of paramagnetic NMR spectra may be used to gain insight into the spin crossover (SCO) properties of iron(II)-based metal organic coordination cages, specifically examining how the structure of the local metal coordination environment affects SCO. To represent the tetrahedral metal-organic cage, a model system is generated by considering an isolated metal-ion vertex: fac-ML3(2+) (M = Fe(II), Co(II); L = N-phenyl-2-pyridinaldimine). The sensitivity of the (1)H paramagnetic chemical shifts to local coordination environments is assessed and utilised to shed light on spin crossover behaviour in iron complexes. Our data indicate that expansion of the metal coordination sphere must precede any thermal SCO. An attempt to correlate experimental enthalpies of SCO with static properties of bound guests shows that no simple relationship exists, and that effects are likely due to nuanced dynamic response to encapsulation.

Lanthanide-Loaded Erythrocytes As Highly Sensitive Chemical Exchange Saturation Transfer MRI Contrast Agents

Chemical exchange saturation transfer (CEST) agents are a new class of frequency-encoding MRI contrast agents with a great potential for molecular and cellular imaging. As for other established MRI contrast agents, the main drawback deals with their low sensitivity. The sensitivity issue may be tackled by increasing the number of exchanging protons involved in the transfer of saturated magnetization to the "bulk" water signal. Herein we show that the water molecules in the cytoplasm of red blood cells can be exploited as source of exchangeable protons provided that their chemical shift is properly shifted by the intracellular entrapment of a paramagnetic shift reagent. The sensitivity of this system is the highest displayed so far among CEST agents (less than 1 pM of cells), and the natural origin of this system makes it suitable for in vivo applications. The proposed Ln-loaded RBCs may be proposed as reporters of the blood volume in the tumor region.

A 23Na Magic Angle Spinning Nuclear Magnetic Resonance, XANES, and High-Temperature X-ray Diffraction Study of NaUO3, Na4UO5, and Na2U2O7

The valence state of uranium has been confirmed for the three sodium uranates NaU(V)O3/[Rn](5f(1)), Na4U(VI)O5/[Rn](5f(0)), and Na2U(VI)2O7/[Rn](5f(0)), using X-ray absorption near-edge structure (XANES) spectroscopy. Solid-state (23)Na magic angle spinning nuclear magnetic resonance (MAS NMR) measurements have been performed for the first time, yielding chemical shifts at -29.1 (NaUO3), 15.1 (Na4UO5), and -14.1 and -19 ppm (Na1 8-fold coordinated and Na2 7-fold coordinated in Na2U2O7), respectively. The [Rn]5f(1) electronic structure of uranium in NaUO3 causes a paramagnetic shift in comparison to Na4UO5 and Na2U2O7, where the electronic structure is [Rn]5f(0). A (23)Na multi quantum magic angle spinning (MQMAS) study on Na2U2O7 has confirmed a monoclinic rather than rhombohedral structure with evidence for two distinct Na sites. DFT calculations of the NMR parameters on the nonmagnetic compounds Na4UO5 and Na2U2O7 have permitted the differentiation between the two Na sites of the Na2U2O7 structure. The linear thermal expansion coefficients of all three compounds have been determined using high-temperature X-ray diffraction: αa = 22.7 × 10(-6) K(-1), αb = 12.9 × 10(-6) K(-1), αc = 16.2 × 10(-6) K(-1), and αvol = 52.8 × 10(-6) K(-1) for NaUO3 in the range 298-1273 K; αa = 37.1 × 10(-6) K(-1), αc = 6.2 × 10(-6) K(-1), and αvol = 81.8 × 10(-6) K(-1) for Na4UO5 in the range 298-1073 K; αa = 6.7 × 10(-6) K(-1), αb = 14.4 × 10(-6) K(-1), αc = 26.8 × 10(-6) K(-1), αβ = -7.8 × 10(-6) K(-1), and αvol = -217.6 × 10(-6) K(-1) for Na2U2O7 in the range 298-573 K. The α to β phase transition reported for the last compound above about 600 K was not observed in the present studies, either by high-temperature X-ray diffraction or by differential scanning calorimetry.

Solid State 13C and 2H NMR Investigations of Paramagnetic [Ni(II)(acac)2L2] Complexes

Nine structurally related paramagnetic acetylacetonato nickel(II) complexes: [Ni(acac)2] and trans-[Ni(acac)2(X)2]nH/D2O, X = H2O, D2O, NH3, MeOH, PMePh2, PMe2Ph, or [dppe]1/2, n = 0 or 1, dppe = 1,2-bis(diphenylphosphino)ethane, as well as cis-[Ni(F6-acac)2(D2O)2], F6-acac = hexafluoroacetylonato, have been characterized by solid state (13)C MAS NMR spectroscopy. (2)H MAS NMR was used to probe the local hydrogen bonding network in [Ni(acac)2(D2O)2]D2O and cis-[Ni(F6-acac)2(D2O)2]. The complexes serve to benchmark the paramagnetic shift, which can be associated with the resonances of atoms of the coordinated ligands. The methine (CH) and methyl (CH3) have characteristic combinations of the isotropic shift (δ) and anisotropy parameters (d, η). The size of the anisotropy (d), which is the sum of the chemical shift anisotropy (CSA) and the paramagnetic electron-nuclei dipolar coupling, is much more descriptive than the isotropic shift. Moreover, the CSA is found to constitute up to one-third of the total anisotropy and should be taken into consideration when (13)C anisotropies are used for structure determination of paramagnetic materials. The (13)C MAS NMR spectra of trans-[Ni(acac)2(PMe2Ph)2], trans-[Ni(acac)2(PMePh2)2], and the noncrystallographically characterized trans-[Ni(acac)2(dppe)]n were assigned using these correlations. The complexes with L = H2O, D2O, NH3, and MeOH can be prepared by a series of solid state desorption and sorption reactions. Crystal structures for trans-[Ni(acac)2(NH3)2] and trans-[Ni(acac)2(PMePh2)2] are reported.

Protonolysis of Fe–C bonds of a diiminopyridineiron(II) dialkyl complex by acids of different strengths: Influence of monoanionic ligands on the spectroscopic properties of diiminopyiridine-FeY2 complexes

The reaction of the dialkyliron complex [Fe(CH2SiMe3)2(MesBIP)] (MesBIP=2,6-bis((N-mesityl)acetimidoyl)pyridine) with protic acids (HY) of different strengths (Y=C6F5O, CF3CO2, Cl, CF3SO3) invariably leads to the cleavage of both Fe–C bonds, independent of the Fe/HY ratio used (either 1:2 or 1:1), affording the corresponding complexes [FeY2(MesBIP)]. Relevant spectroscopic features of these compounds, such as paramagnetic 1H NMR shifts and UV–Vis absorption bands, exhibit a marked dependence on the nature of Y.

Average and Local Structural Origins of the Optical Properties of the Nitride Phosphor La3–xCexSi6N11 (0 < x ≤ 3)

Structural intricacies of the orange-red nitride phosphor system La(3-x)Ce(x)Si6N11 (0 < x ≤ 3) have been elucidated using a combination of state-of-the art tools, in order to understand the origins of the exceptional optical properties of this important solid-state lighting material. In addition, the optical properties of the end-member (x = 3) compound, Ce3Si6N11, are described for the first time. A combination of synchrotron powder X-ray diffraction and neutron scattering is employed to establish site preferences and the rigid nature of the structure, which is characterized by a high Debye temperature. The high Debye temperature is also corroborated from ab initio electronic structure calculations. Solid-state (29)Si nuclear magnetic resonance, including paramagnetic shifts of (29)Si spectra, are employed in conjunction with low-temperature electron spin resonance studies to probes of the local environments of Ce ions. Detailed wavelength-, time-, and temperature-dependent luminescence properties of the solid solution are presented. Temperature-dependent quantum yield measurements demonstrate the remarkable thermal robustness of luminescence of La2.82Ce0.18Si6N11, which shows little sign of thermal quenching, even at temperatures as high as 500 K. This robustness is attributed to the highly rigid lattice. Luminescence decay measurements indicate very short decay times (close to 40 ns). The fast decay is suggested to prevent strong self-quenching of luminescence, allowing even the end-member compound Ce3Si6N11 to display bright luminescence.

31P Magic Angle Spinning NMR Study of Flux-Grown Rare-Earth Element Orthophosphate (Monazite/Xenotime) Solid Solutions: Evidence of Random Cation Distribution from Paramagnetically Shifted NMR Resonances

We present (31)P magic angle spinning nuclear magnetic resonance spectra of flux-grown solid solutions of La(1-x)Ce(x)PO4 (x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y(1-x)M(x)PO4 (M = V(n+), Ce(3+), Nd(3+), x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic V(n+), Ce(3+), and Nd(3+) in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensities of these peaks are related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La(3+) or Y(3+) with the paramagnetic substitutional species Ce(3+) and Nd(3+). The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the (31)P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

Temperature-dependent 29Si NMR resonance shifts in lightly- and heavily-doped Si:P

Careful NMR measurements on a very lightly-doped reference silicon sample provide a convenient highly precise and accurate secondary chemical shift reference standard for 29Si MAS-NMR applicable over a wide temperature range. The linear temperature-dependence of the 29Si chemical shift measured in this sample is used to refine an earlier presentation of the paramagnetic (high-frequency) 29Si resonance shifts in heavily-doped n-type silicon samples near the metal–nonmetal transition. The data show systematic decreases of the local magnetic fields with increasing temperature in the range 100–470K for all samples in the carrier concentration range from 2×1018cm−3 to 8×1019cm−3. This trend is qualitatively similar to that previously observed for the two-orders of magnitude larger 31P impurity NMR resonance shifts in the same temperature and concentration ranges. The 29Si and 31P resonance shifts are not related by a simple scaling factor, however, indicating that impurity and host nuclei are affected by different subsets of partially-localized extrinsic electrons at all temperatures.

19F NMR Studies of a Desolvated Near-Native Protein Folding Intermediate

Although many proteins are recognized to undergo folding via an intermediate, the microscopic nature of folding intermediates is less understood. In this study, ¹⁹F NMR and near-UV circular dichroism (CD) are used to characterize a transition to a thermal folding intermediate of calmodulin, a water-soluble protein, which is biosynthetically enriched with 3-fluorophenylalanine (3F-Phe). ¹⁹F NMR solvent isotope shifts, resulting from replacing H₂O with D₂O, and paramagnetic shifts arising from dissolved O₂ are used to monitor changes in the water accessibility and hydrophobicity of the protein interior as the protein progresses from a native state to an unfolded state along a heat-denaturation pathway. In comparison to the native state, the solvent isotope shifts reveal the decreased presence of water in the hydrophobic core, whereas the paramagnetic shifts show the increased hydrophobicity of this folding intermediate. ¹⁵N, ¹H and methyl ¹³C,¹H HSQC NMR spectra demonstrate that this folding intermediate retains a near-native tertiary structure whose hydrophobic interior is highly dynamic. ¹⁹F NMR CPMG relaxation dispersion measurements suggest the near-native state is transiently adopted well below the temperature associated with its onset.

β2‐Adrenergic Receptor Activation by Agonists Studied with 19F NMR Spectroscopy

β₂‐Adrenergic Receptor Activation by Agonists Studied with ¹⁹F NMR Spectroscopy

Paramagnetic properties of the low- and high-spin states of yeast cytochrome c peroxidase

Here we describe paramagnetic NMR analysis of the low- and high-spin forms of yeast cytochrome c peroxidase (CcP), a 34kDa heme enzyme involved in hydroperoxide reduction in mitochondria. Starting from the assigned NMR spectra of a low-spin CN-bound CcP and using a strategy based on paramagnetic pseudocontact shifts, we have obtained backbone resonance assignments for the diamagnetic, iron-free protein and the high-spin, resting-state enzyme. The derived chemical shifts were further used to determine low- and high-spin magnetic susceptibility tensors and the zero-field splitting constant (D) for the high-spin CcP. The D value indicates that the latter contains a hexacoordinate heme species with a weak field ligand, such as water, in the axial position. Being one of the very few high-spin heme proteins analyzed in this fashion, the resting state CcP expands our knowledge of the heme coordination chemistry in biological systems.