Cross-Polarization Solid-State NMR Quantification of Species within Pores of Metal-Organic Frameworks: A Case Study of α-Mg3(HCOO)6.

The quantitative measurement of adsorbed guest species within metal-organic framework (MOF) pores is of fundamental importance for evaluating the adsorption performance of MOFs. However, routine analytic techniques such as thermogravimetric analysis cannot distinguish the contribution from species adsorbed within pores, species adsorbed on the surface, and gas phase or liquid phase encapsulated in the inter-crystalline space. Herein, we developed a new quantification method based on the cross-polarization (CP) solid-state nuclear magnetic resonance (ssNMR) technique, in which only the species within MOF pores are selectively probed due to the dramatically reduced mobility. Using the commercialized MOF α-Mg3(HCOO)6 as an example, a good linear correlation between Areaguest/Areaframework (i. e., the integrated area of guest and framework 13C NMR signals) and guest loading can be observed for several representative molecules such as benzene, tetrahydrofuran (THF), and 1,4-dioxane, clearly revealing the feasibility of CP quantification approach. The effects of guest molecule and corresponding residual mobility on the CP quantification are further discussed by varying the geometry and size of guest molecules. This methodology thus provides an effective and irreplaceable route to evaluate the adsorption performance of porous materials in-depth, especially for liquid-phase adsorption and gas-phase adsorption in which the capillary condensation is not negligible.

Carbon-detected deuterium solid-state NMR rotating frame relaxation measurements for protein methyl groups under magic angle spinning.

Deuterium rotating frame solid-state NMR relaxation measurements (2H R1ρ) are important tools in quantitative studies of molecular dynamics. We demonstrate how 2H to 13C cross-polarization (CP) approaches under 10-40 kHz magic angle spinning rates can be combined with the 2H R1ρ blocks to allow for extension of deuterium rotating frame relaxation studies to methyl groups in biomolecules. This extension permits detection on the 13C nuclei and, hence, for the achievement of site-specific resolution. The measurements are demonstrated using a nine-residue low complexity peptide with the sequence GGKGMGFGL, in which a single selective -13CD3 label is placed at the methionine residue. Carbon-detected measurements are compared with the deuterium direct-detection results, which allows for fine-tuning of experimental approaches. In particular, we show how the adiabatic respiration CP scheme and the double adiabatic sweep on the 2H and 13C channels can be combined with the 2H R1ρ relaxation rates measurement. Off-resonance 2H R1ρ measurements are investigated in addition to the on-resonance condition, as they extent the range of effective spin-locking field.

Effect of different instrumental techniques and clinical experience on shade matching.

PURPOSE: Many factors can affect the aesthetics of dental restorations, including the instrumental techniques used in shade matching, and can lead to clinical failure. The aim of this study was to investigate the effectiveness of using the cross-polarization digital photograph technique and intraoral scanners for shade matching, and also evaluate the effect of the level of clinical experience on shade matching success. MATERIALS AND METHODS: Color analysis was performed on the maxillary right central incisors of 10 subject models with Vita Easyshade. Intraoral scanning was performed 10 times on each model using TRIOS 3 and color analysis was performed from the same spot. Then cross-polarized and non-polarized photographs of the models were taken with standard settings using a gray reference card. Each shade tab of the Vita System 3D-Master scale was also photographed with two different polarization techniques. Four groups (n = 12), including prosthodontics faculty staff, postgraduate students in prosthodontics, undergraduate students, and dental technicians matched the shade tabs and the model photographs obtained with both techniques on a standardized computer screen. Finally, the color differences between the shade tabs and maxillary central incisors matched by observers from four different groups were recorded using a colorimeter, Classic Color Meter, in accordance with the CIELAB system and CIEDE2000 (ΔE00) values were calculated. The data were compared with the acceptability threshold of 1.80 for ΔE00. The data obtained from the observers were analyzed with IBM SPSS Statistics 26.0 Release Notes program. Independent Samples t-test was used to compare normally distributed data according to binary groups. The level of significance was 0.05. RESULTS: A statistically significant difference was found in the shade matching on photographs taken with different techniques in postgraduate students (p = 0.02). Also, there was a statistically significant difference in success between the groups that made shade matching based on photographs obtained with the non-polarization technique (p = 0.00). The undergraduate students achieved statistically significantly lower results than all other groups (ΔE00 = 5.57 ± 1.07). The kappa value between the intraoral scanner and spectrophotometer results was 0.10, and this value was not statistically significant (p = 0.32). CONCLUSIONS: The cross-polarization technique used especially for shade matching is not superior to the non-polarization technique. Academic and clinical experience might be correlated with shade-matching success with the non-polarization technique. The clinical acceptability threshold could not be achieved in the shade matchings made on digital photographs taken with both techniques. Shade matching performed with an intraoral scanner did not yield reliable results.

Strategies for acquisition of resonance assignment spectra of highly dynamic membrane proteins: a GPCR case study.

In protein nuclear magnetic resonance (NMR), chemical shift assignment provides a wealth of information. However, acquisition of high-quality solid-state NMR spectra depends on protein-specific dynamics. For membrane proteins, bilayer heterogeneity further complicates this observation. Since the efficiency of cross-polarization transfer is strongly entwined with protein dynamics, optimal temperatures for spectral sensitivity and resolution will depend not only on inherent protein dynamics, but temperature-dependent phase properties of the bilayer environment. We acquired 1-, 2-, and 3D homo- and heteronuclear experiments of the chemokine receptor CCR3 in a 7:3 phosphatidylcholine:cholesterol lipid environment. 1D direct polarization, cross polarization (CP), and T2' experiments indicate sample temperatures below - 25 °C facilitate higher CP enhancement and longer-lived transverse relaxation times. T1rho experiments indicate intermediate timescales are minimized below a sample temperature of - 20 °C. 2D DCP NCA experiments indicated optimal CP efficiency and resolution at a sample temperature of - 30 °C, corroborated by linewidth analysis in 3D NCACX at - 30 °C compared to - 5 °C. This optimal temperature is concluded to be directly related the lipid phase transition, measured to be between - 20 and 15 °C based on rINEPT signal of all-trans and trans-gauche lipid acyl conformations. Our results have critical implications in acquisition of SSNMR membrane protein assignment spectra, as we hypothesize that different lipid compositions with different phase transition properties influence protein dynamics and therefore the optimal acquisition temperature.

Kinetics of 1H →31P NMR cross-polarization and dynamics in a layered crystalline α-Sn(IV) phosphate.

The proton-phosphorus (H-P) cross-polarization (CP) is effective in Sn(HPO4)2·H2O despite of the presence of paramagnetic ion impurities. Polarization constants TH-P and 1H T1ρ times are measured in static Sn(HPO4)2·H2O by the kinetic variable-temperature H-P CP experiments. The temperature dependence of the 1H T1ρ times is interpreted in terms of proton movements in the interlayer space occurring between the phosphate groups without participation of the water molecules. The process requires an activation energy of 8.7 ± 0.7 kcal/mol. The MAS effect on the 1H T1ρ times is shown and discussed.

Indirectly detected satellite-transition quadrupolar NMR via progressive saturation of the proton reservoir.

Static satellite-transitions (ST) NMR line shapes from half-integer quadrupolar nuclei could be very informative: they can deliver insight about local motions over a wide range of timescales, and can report on small changes in the local electronic environments as reflected by variations in the quadrupolar parameters. Satellite transitions, however, are typically "invisible" for half-integer quadrupolar nuclei due to their sheer breadth, leading to low signal-to-noise ratio -especially for unreceptive low-gamma or dilute quadrupolar nuclei. Very recently we have introduced a method for enhancing the NMR sensitivity of unreceptive X nuclei in static solids dubbed PROgressive Saturation of the Proton Reservoir (PROSPR), which opens the possibility of magnifying the signals from such spins by repeatedly imprinting frequency-selective X-driven depolarizations on the much more sensitive 1H NMR signal. Here, we show that PROSPR's efficacy is high enough for enabling the detection of static ST NMR for challenging species like 35Cl, 33S and even 17O -all at natural-abundance. The ensuing ST-PROSPR NMR experiment thus opens new approaches to probe ultra-wideline (6-8 MHz wide) spectra. These highly pronounced anisotropies can in turn deliver new vistas about dynamic changes in solids, as here illustrated by tracking ST line shapes as a function of temperature during thermally-driven events.

Sensitivity considerations on denoising series of spectra by singular value decomposition.

When acquiring series of spectra ( T 1 , T 2 , CP buildup curves, etc.) on samples with poor SNR, we are usually faced with choosing between taking a few points with a large number of scans to maximize the SNR or more points with a smaller number of scans to maximize the information content. In this Letter, we show how low-rank decomposition can be used to denoise a series of spectra, reducing the trade-off between the number of scans and the number of experiments.

Gain Enhancement and Cross-Polarization Suppression of Cavity-Backed Antennas Using a Flared Ground Cavity and Iris.

Herein, we present new design principles for gain enhancement and cross-polarization suppression in dual-polarized cavity-backed antennas and demonstrate the capability in an octagonal cavity-backed open prism antenna (OCROP). In our approach, the gain is enhanced through an optimal flaring procedure and a novel metallic iris is used to control the electromagnetic fields and thereby reduce the cross-polarization. Previously, we investigated a dual-polarized OCROP antenna configuration and were able to simultaneously achieve 50% impedance bandwidth, 40% cross-polarization bandwidth (≤25 dB), and 10.2 dBi peak gain. In this study, we investigated gain enhancement by flaring an upper section of the ground cavity sidewalls, while maintaining a constant cavity height. Two cases were investigated: (1) the flare angle was modified, while the ratio of the non-flared to flared sidewall heights was kept constant, and (2) the ratio of the non-flared to flared sidewall heights was varied. In case 1, we established that, while increasing the flare angle results in a gain increase, there is a limit, as cross-polarization at the upper operating frequencies increases. In case 2, we were able to reduce the aperture phase error and achieve a higher peak gain of 12.8 dBi. To address the increased cross-polarization at the high frequency end when a large flare was used, we added a metallic iris at the junction of non-flared and flared sidewalls. We showed that increasing the iris width generally decreases the cross-polarization at high frequencies, without compromising the gain and impedance bandwidth. At an optimal width, it provides a nearly constant, low cross-polarization (below -25.8 dB) and a peak gain of 13.3 dBi, across the entire 50.7% impedance bandwidth of the antenna. We fabricated and successfully tested a prototype to verify the design and simulation approach. These results prove that incorporating an aperture flare with a metallic iris can significantly improve the gain and cross-polarization performance of cavity-backed antennas.

Wideband Dual-Polarized Octagonal Cavity-Backed Antenna with Low Cross-Polarization and High Aperture Efficiency.

Simultaneously enhancing multiple antenna performance parameters is a demanding task, especially with a challenging set of design goals. In this paper, by carefully deriving a compatible set of enhancement techniques, we propose a compact/lightweight/low-cost high-performance L-band octagonal cavity-backed hybrid antenna with multiple attractive features: dual-polarization, wide impedance bandwidth, low cross-polarization, high gain, and high aperture efficiency. The ground cavity is octagonal, which allows the antenna to have a small footprint, and, more importantly, low cross-polarization and high aperture efficiencies when compared to a commonly-used square design. The hybrid design relies on the resonance merging of two radiating elements, i.e., radiating feedlines and a conductive open prism, to form a wide impedance bandwidth. To permit polarization diversity and low cross-polarization, it is differentially and orthogonally fed. Herein, a series of parametric simulation studies on antenna configurations provide information on how to improve the impedance bandwidth and cross-polarization performance. To verify the simulation studies, an antenna prototype was fabricated and tested. Excellent agreement between the simulated and measured results was reached.

Cross-Polarization Schemes for Improved Heteronuclear Transfers Involving Labile Protons in Biomolecular Solution NMR.

INEPT-based experiments are widely used for 1 H→15 N transfers, but often fail when involving labile protons due to solvent exchanges. J-based cross polarization (CP) strategies offer a more efficient alternative to perform such transfers, particularly when leveraging the Hwater ↔ ${ \leftrightarrow }$ HN exchange process to boost the 1 H→15 N transfer process. This leveraging, however, demands the simultaneous spin-locking of both Hwater and HN protons by a strong 1 H RF field, while fulfilling the γH B1,H =γN B1,N Hartmann-Hahn matching condition. Given the low value of γN /γH , however, these demands are often incompatible-particularly when experiments are executed by the power-limited cryogenic probes used in contemporary high field NMR. The present manuscript discusses CP alternatives that can alleviate this limitation, and evaluates their performance on urea, amino acids, and intrinsically disordered proteins. These alternatives include new CP variants based on frequency-swept and phase-modulated pulses, designed to simultaneously fulfill the aforementioned conflicting conditions. Their performances vis-à-vis current options are theoretically analyzed with Liouville-space simulations, and experimentally tested with double and triple resonance transfer experiments.

Elucidating structure and dynamics of crystalline α-zirconium phosphates intercalated with water and methanol by multinuclear solid-state MAS NMR: A comprehensive NMR approach.

Solid-state NMR experiments on 2 H, 31 P, 13 C, and 1 H nuclei, including 31 P T1 , 1 H T1 , and 1 H T1ρ measurements, as well as on the kinetics of proton-phosphorus cross-polarization have been performed to characterize the crystalline and amorphous α-zirconium phosphates, which were intercalated with D2 O and/or CD3 OD. The 13 C{1 H} CP MAS NMR experiment performed for compound 1-CD3 OD (Zr (HPO4 )2. 0.2CD3 OD) with carbon cross-polarization via protons of phosphate groups has provided a prove that the methanol was intercalated into the interlayer spaces of this compound. The variable-temperature 2 H solid-echo MAS NMR spectra of intercalated compounds demonstrated that the methanol molecules, in contrast to the mobile water, were immobile, keeping, however, free CD3 rotations around the C3 -axis. It has been demonstrated that the intercalated species, D2 O and CD3 OD, do not affect the high-frequency motions of the phosphate groups. By utilizing local structural models that satisfy the constraints of the experimental data, it has been suggested that the immobile methanol molecules are located in the cavity between two neighboring layers of the zirconium phosphates. Thus, the present work illustrates the reliable criteria in a comprehensive NMR approach to structural and dynamic studies of such systems.

Hyperpolarization via dissolution dynamic nuclear polarization: new technological and methodological advances.

Dissolution-DNP is a method to boost liquid-state NMR sensitivity by several orders of magnitude. The technique consists in hyperpolarizing samples by solid-state dynamic nuclear polarization at low temperature and moderate magnetic field, followed by an instantaneous melting and dilution of the sample happening inside the polarizer. Although the technique is well established and the outstanding signal enhancement paved the way towards many applications precluded to conventional NMR, the race to develop new methods allowing higher throughput, faster and higher polarization, and longer exploitation of the signal is still vivid. In this work, we review the most recent advances on dissolution-DNP methods trying to overcome the original technique's shortcomings. The review describes some of the new approaches in the field, first, in terms of sample formulation and properties, and second, in terms of instrumentation.

[Study of the structure and microflora of urethral tissues in urethral pain syndrome].

Urethral pain syndrome (UPS) is characterized by the occurrence of persistent or recurrent pain in the urethra in the absence of a confirmed infection and other obvious local pathological changes. The study of its pathogenetic aspects is important first of all for understanding the causes of the disease, to prescribe effective treatment, specific recommendations for the prevention and treatment of this disease are also absent. This paper presents the advanced experience of our research group on the study of the urethral state by the in vivo cross-polarization optical coherence tomography (CP OCT) method, and also the results of the microbiota analysis in the urethral tissues. The purpose of the study is to search for the risk factors for UPS and the character of changes in the urethral tissues, using the data of: 1) concomitant pathology, 2) structural changes in the urethral wall in UPS in comparison with chronic cystitis of bacterial etiology 3) studying the microbiota of urethral tissues. MATERIALS AND METHODS: The condition of the urethra was studied in 109 patients: 55 of them with UPS (group "US"), without clinical manifestations of inflammation; 41 - with chronic inflammation of the lower urinary tract of various origins (group "Inf"); in 14 patients with stones of the upper urinary tract without pyelonephritis, the urethra was taken as the norm (group "N"). All performed a clinical minimum of studies, also cystoscopy with the study of the bladder triangle, the neck of the bladder and the urethra by the method of in vivo tissue imaging - CP OCT. The device "OCT-1300U" with wavelength of 1300 nm is used. To determine the possible role of UPS disease background, the analysis of concomitant pathology preceding the development of UPS was performed. To analyze the relationship of changes in the urethral tissues with the composition of its microbiota, a PCR study of biopsies from the proximal segment of the urethra was performed in 13 patients with UPS. RESULTS: Qualitative comparison of the thickness and character of the OCT signal of the urethral wall layers observed using CP OCT in the studied groups of patients allowed us to establish that the state of the epithelium and connective tissue structures of the mucous membrane in patients with UPS is not the norm, changes are similar to those in chronic inflammation. Changes in the character of the OCT signal were recorded in all parts of the urethra, but in the middle third they are most pronounced and most critical. In UPS, there is a brightly pronounced reorganization of the connective tissue stroma components. Pronounced fibrosis of subepithelial structures (increased signal brightness in the cross-channel compared to the norm) with their thickening was recorded in 48.2% of cases, and thinning/lack of visualization of the epithelial layer was detected in 20.5%, and in chronic inflammation 55.5% and 40.6% of cases, respectively. According to the results of PCR, only one patient had significant total bacterial contamination of the biopsy (TB=104.7). In all other cases, the total bacterial mass of the biopsies was at the level of negative control. CONCLUSIONS: In patients with UPS, the presence of several concomitant, often chronic, diseases was revealed, which may be a premorbid background and one of the risk factors for the occurrence and maintenance of UPS. Pilot PCR studies of biopsies from the proximal segment of the urethra indicate that low values of bacterial contamination in the majority of patients with UPS do not exclude the possible role of bacteria in the development of the disease in some patients. The CP OCT method used in this study is currently the only one in vivo method of visualization of the urethral mucosa, which provides real-time images of structural changes in the epithelial (atrophy or hyperplasia) and connective tissue (active or latent inflammation with cellular infiltration or fibrosis) layers of the urethra, allowing better understanding of the pathogenesis of the disease and monitoring of therapy.

MAS NMR detection of hydrogen bonds for protein secondary structure characterization.

Hydrogen bonds are essential for protein structure and function, making experimental access to long-range interactions between amide protons and heteroatoms invaluable. Here we show that measuring distance restraints involving backbone hydrogen atoms and carbonyl- or α-carbons enables the identification of secondary structure elements based on hydrogen bonds, provides long-range contacts and validates spectral assignments. To this end, we apply specifically tailored, proton-detected 3D (H)NCOH and (H)NCAH experiments under fast magic angle spinning (MAS) conditions to microcrystalline samples of SH3 and GB1. We observe through-space, semi-quantitative correlations between protein backbone carbon atoms and multiple amide protons, enabling us to determine hydrogen bonding patterns and thus to identify ß-sheet topologies and α-helices in proteins. Our approach shows the value of fast MAS and suggests new routes in probing both secondary structure and the role of functionally-relevant protons in all targets of solid-state MAS NMR.

1H, 29Si and 119Sn double and triple resonance NMR spectroscopy of the small-pore framework sodium stannosilicate Na2SnSi3O9·2H2O.

The small-pore framework sodium stannosilicate AV-10, chemical composition Na2SnSi3O9·2H2O and known crystallographic structure, was synthesized by hydrothermal crystallization. This stannosilicate is built up of a three-dimensional network of corner-shared SiO4 tetrahedra and SnO6 octahedra. The SnO6 sites are linked to six SiO4 tetrahedra (Sn(6Si)) while each of the two crystallographically different SiO4 units are connected to two SnO6 and SiO4 units (Si(2Si,2Sn)). This material was used as model compound for developing a solid-state MAS NMR strategy aimed on the challenges and possibilities for structural studies, particularly considering the short and medium range order to verify the connectivity of SiO4 and SnO6 of such compounds despite the low natural abundances of 4.68% for 29Si and 8.59% for 119Sn nuclei as a real challenge. 29Si{119Sn} and 119Sn{29Si} REDOR (Rotational-Echo Double-Resonance) NMR measurements after 1H cross-polarization (CP) were carried out. The REDOR curves show a significant change after the "normal" quadratic short time evolution from which both (i) the shortest internuclear 29Si - 119Sn distances (and vice versa) and (ii) the number of corner-sharing SiO4 tetrahedra around the SnO6 octahedra (and vice versa) can be obtained. Based on these data, optimized 29Si{119Sn} and 119Sn{29Si} REPT-HMQC (Recoupled Polarization Transfer-Heteronuclear Multiple-Quantum Correlation, again after 1H CP) experiments were implemented, which directly show those heterogroup connectivity as correlation peaks in a 2D spectrum. This information was also obtained using 2D29Si{119Sn}-J-Coupling NMR experiments. Furthermore, 2D29Si INADEQUATE NMR experiments are also feasible, showing the connectivity of SiO4 tetrahedra. The combination of REDOR, REPT-HMQC, J-Coupling and INADEQUATE experiments yielded a complete analysis of the short and medium range structure of this microporous stannosilicate, in agreement with the previously published structure obtained Ab Initio from powder X-Ray diffraction data (XRD).

Ultrawideband, Wide Scanning Stripline-Fed Tightly Coupled Array Antenna Based on Parallel-Dipole Elements.

A stripline-fed tightly coupled array antenna with compact size, large scan volume and low cross-polarization characteristics is proposed for ultrawideband (UWB) applications. Simple impedance-matching process is realized by using parallel dual dipoles. Meanwhile, the parallel symmetrical radiating structures minimize the cross-polarization field components dramatically. The mitigation of various undesired resonances is studied in detail. An infinite array is designed to achieve 3:1 bandwidth (6-18 GHz) when scanning ±60∘ in the E-/D-planes (VSWR < 2.5) and H-plane (VSWR < 3.5). The cross-polarization levels remain below -29 dB at broadside. A 16 × 16 prototype is fabricated to demonstrate the design. The measured results are consistent well with the simulated ones. The overall size of the prototype at the lowest operating frequency is 3×3×0.4λ03 (15×15×2cm3). Due to its wide bandwidth, good electronic scan performance and compact size, the proposed antenna array is a good candidate for modern wireless platforms.

Evaluating the relationship between tooth color and enamel thickness, using twin flash photography, cross-polarization photography, and spectrophotometer.

OBJECTIVES: To understand (a) the effects of labial enamel on tooth color (b) relationship of color data taken by nonpolarized (NP), cross-polarization photography (CP), and spectrophotometry (SP). MATERIALS AND METHODS: Fifty extracted human maxillary incisors were coated with resin on their palatal surfaces. Their color was measured with NP, CP, and SP and their dimensions were scanned by an intraoral scanner. The labial enamel was removed using a modified selective enamel demineralization technique. Tooth dimensions and color were recorded again. The differences in the labial enamel thickness (ΔT) and color (∆E*00 and ∆L*, ∆a*, ∆b*) were statistically analyzed with the Pearson correlation coefficient and simple linear regression. RESULTS: In CP and SP methods, ΔT and ∆E*00 were weakly to moderately positively correlated (r = .38 and .27). In NP, CP, and SP methods, ∆T and ∆b* are weakly positively correlated (r = .27, .27 and .29). The color data of three measuring methods were highly positively correlated (r > .8). A linear relationship between ∆E*00 and ∆T were found (CP and SP groups). CONCLUSIONS: (a) Thicker labial enamel has a greater impact on tooth color. (b) Reducing labial enamel thickness shifts the tooth color toward yellow. (c) Tooth color measured from the three methods were highly correlated. CLINICAL SIGNIFICANCE: Knowing the relationship between enamel thickness and tooth color, a clinician can better predict the stump shade before tooth preparation. Due to the highly correlated measuring outcomes, it is reasonable to combine these three methods during shade matching.

Quantification of Monomer Units in Insoluble Polymeric Active Pharmaceutical Ingredients Using Solid-State NMR Spectroscopy I: Patiromer.

Although extensive precautions are taken to limit batch-to-batch variation in pharmaceutical manufacturing, differences between lots may still exist, particularly in complex formulations. When polymerization is used in the production process, the potential for varying chain lengths and incorporation of different monomers increases the likelihood of batch-to-batch variation. This poses a significant challenge for demonstrating active pharmaceutical ingredient (API) sameness between the innovator and generic drug under development. Therefore, the ability to accurately analyze and quantify the relative amounts of active ingredients present in a formulated product is critically important. Solid-state nuclear magnetic resonance (SSNMR) spectroscopy was used to identify, quantify, and compare the relative amounts of the three polymer groups in the amorphous block copolymer drug, patiromer (Veltassa®). Techniques such as cross polarization (CP) and magic angle spinning were used to quantify each polymer group while the importance of understanding CP dynamics to obtain quantitative data was also addressed. It was found that the magnetization transfer rate and chemical shift anisotropy for different functional groups present in patiromer play a large role when optimizing parameters for spectral acquisition. Once accounted for, the average patiromer lot contained 90.9%, 7.6%, and 1.5% carboxylate, aromatic, and aliphatic blocks, respectively, with little lot-to-lot variation between different dosage strengths and expiration dates. SSNMR proved to be a sensitive analytical technique for evaluating and quantifying different monomer groups present in patiromer. This procedure may serve as a guide for similar quantitation studies on complex drug products and for demonstrating API sameness during generic drug development.

A Low-Temperature Broadband NMR Probe for Multinuclear Cross-Polarization.

Dissolution dynamic nuclear polarization (D-DNP) probes are usually designed for one or at most two specific nuclei. Investigation of multiple nuclei usually requires manufacturing a number of costly probes. In addition, changing the probe is a time-consuming process since a system that works at low temperature (usually between 1.2 and 4.2 K) must be warmed up, thus increasing the risks of contamination. Here, an efficient apparatus is described for D-DNP designed not only for microwave-enhanced direct observation of a wide range of nuclei S such as 1 H, 13 C, 2 H, 23 Na, and 17 O, but also for cross-polarization (CP) from I=1 H to such S nuclei. Unlike most conventional designs, the tuning and matching circuits are partly immersed in superfluid helium at temperatures down to 1.2 K. Intense radio-frequency (RF) fields with amplitudes on the order of 50 kHz or better can be applied simultaneously to both nuclei I and S using RF amplifiers with powers on the order of 90 and 80 W, respectively, without significant losses of liquid helium. The system can operate at temperatures over a wide range between 1.2 and 300 K.

Design of a local quasi-distributed tuning and matching circuit for dissolution DNP cross polarization.

Dynamic nuclear polarization (DNP) build-up times at low temperature for low-gamma nuclei can be unfavorably long and can be accelerated by transfer of polarization from protons. The efficiency of the cross polarization (CP) depends on the B1-field strengths, the pulse sequence chosen for cross polarization and the sample composition. CP experiments rely on high B1-fields, which typically lead to electrical discharge and breakdown in the circuit. This problem is particularly severe in the low pressure helium atmosphere due to easily ionized helium atoms. The purpose of this study is to identify strategies to minimize voltages across components in a tuning and matching circuit of the coil to avoid electrical discharge during CP experiments. Design equations for three tuning and matching network configurations are derived. The results of the study are then used in the design of a single coil double resonance DNP probe operating at 71.8 MHz (13C frequency) and 285.5 MHz (1H frequency). In the current setup we achieve 28% polarization on 13C in urea with a build-up time of 11.6 min with CP compared to 14% and 53 min by direct polarization using TEMPOL as the radical. Different cross polarization sequences are compared.