In Situ NMR Parameter Monitoring Systems and Methods for Measuring PH and Temperature

Devices and methods are provided for measuring temperatures and pHs of a sample in situ using NMR spectroscopy, and for sealing one or more ends of a capillary tube after a reference material has been added to the capillary tube, which is used in an in situ NMR temperature measurement device. A method for measuring a pH of a sample in situ using NMR spectroscopy includes providing an in situ NMR pH measurement device. This device includes a sample housing member configured to house a target sample, at least one pH sensor configured to exhibit an NMR spectral change due to a change in pH value of the target sample, and a pH sensor containment member configured to house the at least one pH sensor. The target sample is added to the sample housing member. NMR spectra are obtained to then determine the pH of the target sample

Capillary-Tube Package Devices for the Quantitative Performance Evaluation of Nuclear Magnetic Resonance Spectrometers and Pulse Sequences

With the increased sensitivity of modern nuclear magnetic resonance (NMR) spectrometers, the minimum amount needed for chemical-shift referencing of NMR spectra has decreased to a point where a few microliters can be sufficient to observe a reference signal. The reduction in the amount of required reference material is the basis for the NMR Capillary-tube Package (CapPack) platform that utilizes capillary tubes with inner diameters smaller than 150 µm as NMR-tube inserts for external reference standards. It is shown how commercially available electrophoresis capillary tubes with outer diameters of 360 µm are filled with reference liquids or solutions and then permanently sealed by the arc discharge plasma of a commercially available fusion splicer normally employed for joining optical fibers. The permanently sealed capillaries can be used as external references for chemical-shift, signal-to-noise, resolution, and concentration calibration. Combining a number of permanently sealed capillaries to form CapPack devices leads to additional applications such as performance evaluation of NMR spectrometers and NMR pulse sequences. A 10-capillary-tube side-by-side Gradient CapPack device is used in combination with one or two constant gradients, produced by room-temperature shim coils, to monitor the excitation profiles of shaped pulses. One example illustrates the performance of hyperbolic secant (sech) pulses in the EXponentially Converging Eradication Pulse Train (EXCEPT) solvent suppression sequence. The excitation profile of the pulse sequence is obtained in a single gradient NMR experiment. A clustered T1 CapPack device is introduced consisting of a coaxial NMR-tube insert that holds seven capillary tubes filled with aqueous solutions of different concentrations of the paramagnetic relaxation agent copper(ii) sulfate (CuSO4). The different CuSO4 concentrations lead to spin-lattice relaxation times in the seven capillary tubes that cover a range which extends to more than an order of magnitude. Clustered T1 CapPack devices are best suited to quantify the effects that relaxation has on magnetizations and coherences during the execution of NMR experiments, which is demonstrated for the order-of-magnitude T1 insensitivity of signal suppression with EXCEPT

A Fast and Convenient Way to Predict Relaxation during a Frequency-Selective Adiabatic Hyperbolic Secant Pulse (HS1 Sech Pulse)

Frequency-selective inversion of magnetization is often achieved by long, low-power adiabatic RF pulses. Because these pulses can last hundreds of milliseconds, substantial relaxation of magnetization can occur during their application. Recently, a numerical model was introduced that allows an approximation of relaxation during frequency-selective adiabatic pulses for fast-tumbling small molecules in non-viscous solutions using only standard T1 and T2 relaxation times. This model is now extended to conditions in which net magnetization is not at its thermodynamic equilibrium prior to the adiabatic inversion. Simulated and experimental data reveal that the amplitude of net magnetization after an adiabatic inversion with the HS1 hyperbolic secant pulse can be approximated by a linear function of the magnetization before the pulse, depending only on T1 and T2 relaxation. The model presented here is particularly applicable to solvent-suppression sequences that utilize multiple adiabatic inversions, such as the multiple inversion-recovery nulling sequence EXCEPT. Tabulated slope and intercept values for the linear relationship are provided to facilitate a convenient optimization of pulse sequences that utilize HS1 frequency-selective adiabatic inversions

Predicting the Effect of Relaxation during Frequency-Selective Adiabatic Pulses

Adiabatic half and full passages are invaluable for achieving uniform, B1-insensitive excitation or inversion of macroscopic magnetization across a well-defined range of NMR frequencies. To accomplish narrow frequency ranges with adiabatic pulses ( \u3c 100Hz), long pulse durations at low RF power levels are necessary, and relaxation during these pulses may no longer be negligible. A numerical, discrete recursive combination of the Bloch equations for longitudinal and transverse relaxation with the optimized equation for adiabatic angular motion of magnetization is used to calculate the trajectory of magnetization including its relaxation during adiabatic hyperbolic secant pulses. The agreement of computer-calculated data with experimental results demonstrates that, in non-viscous, small-molecule fluids, it is possible to model magnetization and relaxation by considering standard T1 and T2 relaxation in the traditional rotating frame. The proposed model is aimed at performance optimizations of applications in which these pulses are employed. It differs from previous reports which focused on short high-power adiabatic pulses and relaxation that is governed by dipole-dipole interactions, cross polarization, or chemical exchange

Medicinal Thiols: Current Status and New Perspectives

The thiol (-SH) functional group is found in a number of drug compounds and confers a unique combination of useful properties. Thiol-containing drugs can reduce radicals and other toxic electrophiles, restore cellular thiol pools, and form stable complexes with heavy metals such as lead, arsenic, and copper. Thus, thiols can treat a variety of conditions by serving as radical scavengers, GSH prodrugs, or metal chelators. Many of the compounds discussed here have been in use for decades, yet continued exploration of their properties has yielded new understanding in recent years, which can be used to optimize their clinical application and provide insights into the development of new treatments. The purpose of this narrative review is to highlight the biochemistry of currently used thiol drugs within the context of developments reported in the last five years. More specifically, this review focuses on thiol drugs that represent the standard of care for their associated conditions, including N-acetylcysteine, 2,3-meso-dimercaptosuccinic acid, British anti-Lewisite, D-penicillamine, amifostine, and others. Reports of novel dosing regimens, delivery strategies, and clinical applications for these compounds were examined with an eye toward emerging approaches to address a wide range of medical conditions in the future

Exploding Misconceptions: Developing a Culture of Safety through Learner Driven Activities

On the first day of class, many students enter freshman laboratory courses with an opinion that someone else will provide them with everything they need; a mentality often carried over into future courses and workplaces. This presumption causes frustration and unrealistic expectations when not addressed. On the contrary, a first activity of designing a safety contract, continued with an SDS activity, and reinforced by a strict wardrobe expectation refutes the misconception that instructors will hand answers to learners. Rather than providing answers for students, the program provides opportunities to construct appropriate tools establishing individual responsibility, teamwork, and research to develop a culture of safety in the lab. This communication describes safety activities that guide student choices to enhance the culture of safety at Missouri University of Science and Technology (Rolla, MO), State Fair Community College (Sedalia, MO), and Sacred Heart High School (Sedalia, MO)

Piloting Blended Strategies to Resolve Laboratory Capacity Issues in a First-Semester General Chemistry Course

Laboratory capacity is an issue that has plagued education for more than a century. New buildings, late night classes, and virtual laboratories have offered transitory relief at great expense. Missouri University of Science and Technology is employing blended strategies to increase capacity and student success. Blended strategies expand learning workspaces so that learners conduct traditional laboratory activities in both traditional and nontraditional laboratory environments. This article focuses on the proof of concept pilot results from blending the first-semester general chemistry laboratory course, which validate the adoption of this strategy for increasing student volume

EXponentially Converging Eradication Pulse Train (EXCEPT) for Solvent-Signal Suppression in Investigations with Variable T₁ Times

Selective presaturation is a common technique for suppressing excessive solvent signals during proton NMR analysis of dilute samples in protic solvents. When the solvent T1 relaxation time constant varies within a series of samples, parameters for the presaturation sequence must often be re-adjusted for each sample. The EXCEPT (EXponentially Converging Eradication Pulse Train) presaturation pulse sequence was developed to eliminate time consuming pulse-parameter re-optimization as long as the variation in the solvent\u27s T1 remains within an order of magnitude. EXCEPT consists of frequency-selective inversion pulses with progressively decreasing interpulse delays. The interpulse delays were optimized to encompass T1 relaxation times ranging from 1 to 10 s, but they can be easily adjusted by a single factor for other ranges that fall within an order of magnitude with respect to T1. Sequences with different numbers of inversion pulses were tested to maximize suppression while minimizing the number of pulses and thus the total time needed for suppression. The EXCEPT-16 experiment, where 16 denotes the number of inversion pulses, was found satisfactory for many standard applications. Experimental results demonstrate that EXCEPT provides effective T1-insensitive solvent suppression as predicted by the theory. The robustness of EXCEPT with respect to changes in solvent T1 allows NMR investigations to be carried out for a series of samples without the need for pulse-parameter re-optimization for each sample