Dynamic balancing in NMR double rotor system

An exact solution to the problem of dynamic balancing in a NMR double rotor system is presented. This will enable one to perform high speed spinning about two intersecting axes. Double rotation is used in solid state NMR to average away second-order broadening, thus enhancing the resolution of spectra from quadrupolar nuclei in solid state NMR. An exact expression for imbalance due to asymmetric distribution of weights about the rotation axes is provided.     

A spinning thermometer to monitor microwave heating and glass transitions in dynamic nuclear polarization

As previously demonstrated by Thurber and Tycko, the peak position of ⁷⁹Br in potassium bromide (KBr) allows one to determine the temperature of a spinning sample. We propose to adapt the original design by using a compact KBr tablet placed at the bottom of the magic angle spinning rotor, separated from the sample under investigation by a thin disk made of polytetrafluoroethylene (or ‘Teflon’®). This design allows spinning the sample up to at least 16 kHz. The KBr tablet can remain in the rotor when changing the sample under investigation. Calibration in the range of 98 < T < 320 K has been carried out in a static rotor by inserting a platinum thermometer. The accuracy is better than ± 0.9 K, even in the presence of microwave irradiation. Irradiation with 5 W microwaves at 263 GHz leads to a small temperature increase of 3.6 ± 1.4 K in either static or spinning samples. The dynamic nuclear polarization enhancement decreases with increasing temperature, in particular when a frozen glassy sample undergoes a glass transition. Copyright © 2011 John Wiley & Sons, Ltd.     

Heating caused by radiofrequency irradiation and sample rotation in 13C magic angle spinning NMR studies of lipid membranes

Application of rapid sample rotation and radiofrequency irradiation in magic angle spinning (MAS) NMR of lipid bilayers can significantly increase the sample temperature. In this work, we studied the extent of heating during the acquisition of 1H-decoupled 13C MAS spectra of hydrated dimyristoylphosphatidylcholine (DMPC) in the L(alpha) phase. First, we describe a simple procedure for determining the increase in temperature by observing the shift of the 1H water signal. The method is then used to identify and assess the various factors that contribute to the sample heating. The important factors discussed in this paper include: (i) the spinning speed, (ii) the variable-temperature gas pressure, (iii) the rotor geometry, (iv) the power, duration and frequency of the radiofrequency irradiation and (v) the hydration level. A comparison of different heteronuclear decoupling schemes in terms of their ability to produce highly resolved 13C spectra of DMPC is also reported.     

NMR spectra of a microcrystalline protein at 30 kHz MAS

Proteins are not always available in amounts desirable for solid-state magic-angle spinning (MAS) nuclear-magnetic resonance (NMR) spectroscopy. To maximize the signal-to-noise ratio achievable with small samples, the filling factor must be optimized by using small-diameter MAS rotors. These rotors have the added benefit of allowing higher radio frequency field amplitudes during polarization transfer steps and during decoupling periods as well as allowing higher spinning frequencies. We demonstrate the advantages of relatively fast MAS (30 kHz using a 2.5 mm rotor) compared to MAS at 12 kHz for the 10.4 kDa model protein Crh with 93 residues and show that the signal-to-noise ratio in two-dimensional correlation spectra can be significantly improved by taking advantage of optimized pulse sequences available with rapid MAS.     

Two-dimensional (17)O multiple quantum magic-angle spinning NMR of organic solids

We report two-dimensional (2D) (17)O multiple-quantum magic-angle spinning (MQMAS) NMR spectra for four (17)O-labeled organic compounds: [(17)O(2)]-D-alanine (1), potassium hydrogen [(17)O(4)]dibenzoate (2), [(17)O(4)]-D,L-glutamic acid.HCl (3) and [2,4-(17)O(2)]uracil (4). The high spectral resolution observed in the 2D (17)O MQMAS NMR spectra allows extraction of precise (17)O NMR parameters for all crystallographically distinct oxygen sites. We demonstrate that rotor synchronization is important in obtaining high-quality (17)O MQMAS spectra for organic compounds. Several issues related to the potential of (17)O MQMAS NMR for large biomolecular systems are also discussed.     

Critical comments on accuracy of quantitative determination of natural humic matter by solid state (13)C NMR spectroscopy

Structural information of natural organic matter (NOM) at the molecular level is very essential in understanding their nature and reactivity. Nuclear magnetic resonance (NMR) is an excellent tool for estimating the gross chemical composition of the very complex humic matter (HM). A well-known fact is that the solid state ¹³C NMR spectral analysis is very parameter-sensitive especially in the study of the heterogenous HM (e.g. baseline corrections, different pulse techniques and spinning rates of the rotor vs. different disruptive sidebands in the spectra). This being the case, it has been emphasized the importance of qualitative and quantitative analyses for generating as real spectra as possible by means of different pulse and polarization techniques, sampling spinning rates as well as certain correction factors. In the present study a practical accuracy for quantitative determination of NOM type material by solid state ¹³C NMR spectroscopy was assessed using a known HM sample. Different magnetic-field strengths, sampling spinning rates, single and ramped amplitude cross polarization techniques and TOSS pulse sequence were applied for obtaining a more reliable insight into the disruptive effect of the chemical shift anisotropy (CSA), especially the most disturbing first order spinning side bands (SSB). The results demonstrated that the SSB problem is not so significant as sometimes stated, at least in the context of HM samples and in the light of the overall reproducibility and uncertainty connected with the sample itself.     

Investigation of multiaxis molecular motion by off-magic angle spinning deuteron NMR

The relatively new deuteron NMR method of off-axis-magic angle spinning (OMAS) has been extended and used to investigate multiaxis rotational jump motion. Floquet theory is developed for simulating deuteron OMAS spectra with multisite jumps at different rates about noncoincident axes, and efficient procedures are presented for computing the sideband line shapes. It is demonstrated experimentally that reproducible adjustment of the angle between the rotor axis and the static magnetic field is feasible with precision approaching +/- 0.01 degrees. This leads to the reintroduction of a scaled, first-order quadrupole coupling that defines a new kinetic window and makes deuteron OMAS much more sensitive than ordinary magic angle spinning to motion on the kilohertz time scale. Temperature-dependent deuteron OMAS line shapes of octanoic acid/urea-d4 inclusion compound have been recorded and fitted, using least-squares procedures, to provide rates of rotation about both CN and CO bonds. The Arrhenius activation parameters for rotation about CN bonds, Ea = 60.4+/-2.4 kJ/mol and ln(A) = 24.9+/-0.3, agree well with previous values determined by selective inversion experiments. However, OMAS yields Ea = 26.3+/-0.4 kJ/mole and ln(A) = 24.9+/-0.3 for whole-body rotation about the CO bond axis in contrast to previous analysis of static quadrupole echo (QE) line shapes which gave Ea = 22.3+/-0.3 kJ/mole and ln(A) = 24.8+/-0.6 for the same sample. The underlying homogeneous linewidths of OMAS spectra are much smaller than those of QE spectra, and this provides higher precision and less systematic error in the determination of rates.     

分子陀螺的设计、合成与组装

近来,科学家设计和合成了系列分子水平的陀螺。类似于儿童的玩具陀螺仪,这种分子陀螺由一个转子、一个定子框架和连接定子和转子的轴组成。定子框架通过自身的刚性结构为中心转子的转动提供足够的内在自由度,得以对内部的转子实施保护。并使得分子陀螺成为一个理想的分子转子。当转子上有偶极距时,则可能在外来电、磁、光的刺激下进行定向转动,成为分子马达。化学家们通过X射线晶体衍射技术、动态核磁技术、理论计算化学、热力学分析等方法表征了分子陀螺的各种特征,并积极探索其潜在的应用价值。本文着重介绍分子陀螺,以及超分子陀螺仪的发展历史以及研究进展。     

Electrical and ionic conductivity effects on magic-angle spinning nuclear magnetic resonance parameters of CuI

We investigate experimentally and theoretically the effects of two different types of conductivity, electrical and ionic, upon magic-angle spinning NMR spectra. The experimental demonstration of these effects involves (63)Cu, (65)Cu, and (127)I variable temperature MAS-NMR experiments on samples of γ-CuI, a Cu(+)-ion conductor at elevated temperatures as well as a wide bandgap semiconductor. We extend previous observations that the chemical shifts depend very strongly upon the square of the spinning-speed as well as the particular sample studied and the magnetic field strength. By using the (207)Pb resonance of lead nitrate mixed with the γ-CuI as an internal chemical shift thermometer we show that frictional heating effects of the rotor do not account for the observations. Instead, we find that spinning bulk CuI, a p-type semiconductor due to Cu(+) vacancies in nonstoichiometric samples, in a magnetic field generates induced AC electric currents from the Lorentz force that can resistively heat the sample by over 200 °C. These induced currents oscillate along the rotor spinning axis at the spinning speed. Their associated heating effects are disrupted in samples containing inert filler material, indicating the existence of macroscopic current pathways between micron-sized crystallites. Accurate measurements of the temperature-dependence of the (63)Cu and (127)I chemical shifts in such diluted samples reveal that they are of similar magnitude (ca. 0.27 ppm/K) but opposite sign (being negative for (63)Cu), and appear to depend slightly upon the particular sample. This relationship is identical to the corresponding slopes of the chemical shifts versus square of the spinning speed, again consistent with sample heating as the source of the observed large shift changes. Higher drive-gas pressures are required to spin samples that have higher effective electrical conductivities, indicating the presence of a braking effect arising from the induced currents produced by rotating a conductor in a homogeneous magnetic field. We present a theoretical analysis and finite-element simulations that account for the magnitude and rapid time-scale of the resistive heating effects and the quadratic spinning speed dependence of the chemical shift observed experimentally. Known thermophysical properties are used as inputs to the model, the sole adjustable parameter being a scaling of the bulk thermal conductivity of CuI in order to account for the effective thermal conductivity of the rotating powdered sample. In addition to the dramatic consequences of electrical conductivity in the sample, ionic conductivity also influences the spectra. All three nuclei exhibit quadrupolar satellite transitions extending over several hundred kilohertz that reflect defects perturbing the cubic symmetry of the zincblende lattice. Broadening of these satellite transitions with increasing temperature arises from the onset of Cu(+) ion jumps to sites with different electric field gradients, a process that interferes with the formation of rotational echoes. This broadening has been quantitatively analyzed for the (63)Cu and (65)Cu nuclei using a simple model in the literature to yield an activation barrier of 0.64 eV (61.7 kJ/mole) for the Cu(+) ion jumping motion responsible for the ionic conductivity that agrees with earlier results based on (63)Cu NMR relaxation times of static samples.     

In situ solid-state NMR characterization of pharmaceutical materials: An example of drug-polymer thermal mixing

Pharmaceutical amorphous solid dispersions, a multicomponent system prepared by dispersing drug substances into polymeric matrix via thermal and mechanical processes, represent a major platform to deliver the poorly water-soluble drug. Microscopic properties of drug-polymer contacts play mechanistic roles in manipulating long-term physical stability as well as dissolution profiles. Although solid-state nuclear magnetic resonance has been utilized as an indispensable tool to probe structural details, previous studies are limited to ex situ characterizations. Our work provides likely the first documented example to investigate comelting of ketoconazole and polyacrylic acid, as a model system, in an in situ manner. Their physical mixture is melted and mixed in the solid-state nuclear magnetic resonance rotor under magic angle spinning at up to approximately 400 K. Critical structural events of molecular miscibility and interaction have been successfully identified. These results design and evaluate the instrumental and experimental protocols for real-time characterizations of the comelting of pharmaceutical materials.     

Large-scale oligonucleotide synthesizers

The central problem in scaling up oligonucleotide synthesis is to expose each element of a large bed to the same conditions obtaining in very small ones, for the same intervals of time. Our analysis suggests that scale-up is chiefly limited by fluid path length through the bed. By using annular beds in zonal centrifuge rotors of unique design, with fluid flow controlled by combining centrifugal force with differences in physical density between reagents, reagent fronts may be kept exactly perpendicular to the direction of flow in each bed element. Under these conditions, bed volume may be increased by increasing rotor length and diameter. The rotor is lined with polypropylene or Teflon®, and has a thick tempered glass end window. Transparent rotary valves of a unique design allow any of47 reagents to be selected and the direction of flow through the rotor to be controlled. A photodiode spectrophotometer provides complete absorption spectra on fluid in the rotor inlet and outlet lines every4 s, and a large balance weighs effluent from the synthesizer continuously. The entire operation is controlled by a work station, and steps may be programmed by time, absorbance, or reagent mass. Reagents are identified by spectra, and trityls are integrated on line. A detailed time-stamped log file provides a complete record of each synthesis.     

Magic angle spinning NMR with metallized rotors as cylindrical microwave resonators

We introduce a novel design for millimeter wave electromagnetic structures within magic angle spinning (MAS) rotors. In this demonstration, a copper coating is vacuum deposited onto the outside surface of a sapphire rotor at a thickness of 50 nm. This thickness is sufficient to reflect 197‐GHz microwaves, yet not too thick as to interfere with radiofrequency fields at 300 MHz or prevent sample spinning due to eddy currents. Electromagnetic simulations of an idealized rotor geometry show a microwave quality factor of 148. MAS experiments with sample rotation frequencies of ω_r/2π = 5.4 kHz demonstrate that the drag force due to eddy currents within the copper does not prevent sample spinning. Spectra of sodium acetate show resolved ¹³C J‐couplings of 60 Hz and no appreciable broadening between coated and uncoated sapphire rotors, demonstrating that the copper coating does not prevent shimming and high‐resolution nuclear magnetic resonance spectroscopy. Additionally, ¹³C Rabi nutation curves of ω₁/2π = 103 kHz for both coated and uncoated rotors indicate no detrimental impact of the copper coating on radio frequency coupling of the nuclear spins to the sample coil. We present this metal coated rotor as a first step towards an MAS resonator. MAS resonators are expected to have a significant impact on developments in electron decoupling, pulsed dynamic nuclear polarization (DNP), room temperature DNP, DNP with low‐power microwave sources, and electron paramagnetic resonance detection.     

A simple derivation of Vonnegut's equation for the determination of interfacial tension by the spinning drop technique

A simple derivation of Vonnegut's equation for use in the determination of interfacial tension by the spinning drop technique is described. The derivation involves a cylindrical approximation and calculates the kinetic energy of rotation of the system from a consideration of its moment of inertia.     

Theory and Use of Centrifugal Partition Chromatography

Abstract

Centrifugal Partition Chromatography (CPC) is a variant of countercurrent chromatography (CCC). As in CCC, two immiscible liquids are used. The first liquid is the stationary phase, the second is the mobile phase. The liquid stationary phase is held in channels engraved in seveal polychlorotrifluoroethylene (PCTFE) plates. One hundred channels are engraved on each PCTFE plate. Four PCTFE plates are assembled together in a cartridge. Up to 12 cartridges (4800 channels) can be loaded in the rotor of a centrifuge. The centrifugal field, generated by the spinning rotor, holds the stationary phase sufficiently that a mobile phase can be pumped through in (Figure 1). The system is analyzed in detail.     

13C‐TmDOTA as versatile thermometer compound for solid‐state NMR of hydrated lipid bilayer membranes

Recent advances in solid‐state nuclear magnetic resonance (NMR) techniques, such as magic angle spinning and high‐power decoupling, have dramatically increased the sensitivity and resolution of NMR. However, these NMR techniques generate extra heat, causing a temperature difference between the sample in the rotor and the variable temperature gas. This extra heating is a particularly crucial problem for hydrated lipid membrane samples. Thus, to develop an NMR thermometer that is suitable for hydrated lipid samples, thulium‐1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetate (TmDOTA) was synthesized and labeled with ¹³C (i.e., ¹³C‐TmDOTA) to increase the NMR sensitivity. The complex was mixed with a hydrated lipid membrane, and the system was subjected to solid‐state NMR and differential scanning calorimetric analyses. The physical properties of the lipid bilayer and the quality of the NMR spectra of the membrane were negligibly affected by the presence of ¹³C‐TmDOTA, and the ¹³C chemical shift of the complex exhibited a large‐temperature dependence. The results demonstrated that ¹³C‐TmDOTA could be successfully used as a thermometer to accurately monitor temperature changes induced by ¹H decoupling pulses and/or by magic angle spinning and the temperature distribution of the sample inside the rotor. Thus, ¹³C‐TmDOTA was shown to be a versatile thermometer for hydrated lipid assemblies. Copyright © 2015 John Wiley & Sons, Ltd.     

Two-dimensional NMR methods for studying solid polymers

A survey is given about two-dimensional (2D) NMR experiments on solid polymers involving ²H- and ¹³C-NMR. 2D exchange NMR spectra of static samples directly reflect the distribution of rotational angles resulting from ultraslow molecular motions. Typical examples are the chain motion above the glass transition or rotations around a helix axis in semi-crystalline polymers. 2D-Magic angle spinning not only allows the detection of molecular order and motion. By combining rotor synchronized MAS with rotations in spin space the correlation of order and mobility can be studied.     

Variable angle spinning (VAS) experiments for strongly oriented systems: methods development and preliminary results

Variable angle spinning (VAS) experiments provide a useful method for measuring long-range dipolar couplings and obtaining isotropic-anisotropic correlation spectra. These experiments make it possible to obtain correlations between isotropic and anisotropic spectra without altering the chemical composition of the sample. They also allow working with very strongly oriented systems that are not accessible to solution-state techniques. In this communication, we discuss recent hardware developments in our laboratory and show representative data from small molecules in strongly oriented liquid-crystalline samples.     

Pure Isotropic Proton NMR Spectra in Solids using Deep Learning

The resolution of proton solid-state NMR spectra is usually limited by broadening arising from dipolar interactions between spins. Magic-angle spinning alleviates this broadening by inducing coherent averaging. However, even the highest spinning rates experimentally accessible today are not able to completely remove dipolar interactions. Here, we introduce a deep learning approach to determine pure isotropic proton spectra from a two-dimensional set of magic-angle spinning spectra acquired at different spinning rates. Applying the model to 8 organic solids yields high-resolution ¹H solid-state NMR spectra with isotropic linewidths in the 50–400 Hz range.     

Centrifugal Partition Chromatography. I. General Features

Abstract

Centrifugal Partition Chromatography (CPC) is a variant of countercurrent chromatography (CCC). As in CCC, two immiscible liquids are used. The first liquid is the stationary phase, the second is the mobile phase. The liquid stationary phase is held in channels engraved in several polychlorotrifluoroethylene (PCTFE) plates. One hundred channels are engraved on each PCTFE plate. Four PCTFE plates are assembled together in a cartridge. Up to 12 cartridges (4800 channels) can be loaded in the rotor of a centrifuge. The centrifugal field, generated by the spinning rotor, holds the stationary phase sufficiently that a mobile phase can be pumped through it. This system is analyzed in detail. The stationary phase evolution versus time is studied. A complete derivation is made of the relationship linking system pressure to the spin and flow rate as well as to the physico-chemical properties of the two liquids, i.e., density and viscosity.     

Thermal behaviour of teflon/phenolic liners in self-lubricating bearings

The gun system of the M1 series tank rides on a pair of self-aligning spherical bearings that allows the elevation and depression of the cannon. Because these bearings are encapsulated within the rotor housing, periodic lubrication or maintenance is impossible. To overcome this problem self-lubricating bearings were incorporated into the system. There are two basic liner designs, molded and fabric. Molded liners are produced by applying a formulation of teflon and typically asbestos into a phenolic resin, which is applied to the bearing surface, then cured. Fabric liners utilize a woven fabric bonded to the bearing surface, then teflon which is mixed into phenolic resin is applied to the bearing surface and cured. Initial studies of the existing bearing liner were completed to determine the liner composition and establish a baseline or standard to compare thermal and mechanical properties with potential vendors. DSC revealed an average teflon content of 39.53%, which varied significantly throughout the liner. TG analysis showed an asbestos concentration of 12.22%. The remainder of the liner was phenolic resin. Physical testing of the bearing from ?20 to 120?C under normal loading conditions demonstrated excellent thermal stability with little wear. Bearings from each vendor were tested and compared to the standard properties of the baseline bearing. Some properties were difficult to compare or insignificant due to the design differences between molded and fabric liners. The testing program resulted in the qualification of two bearings, which met or exceeded the established standards. Both of these bearings were designed with fabric liners.