Pulse solid-state NMR

We have found that combined solid-state NMR spectroscopy and DPC results can be used to calculate reaction enthalpies which are in close agreement with Moore (15). Furthermore, we find that the degree of conversion can be significantly affected by post reaction thermal processing. We conclude that the single pulse solid-state NMR spectroscopy can provide reliable, reproducible, and quantitative information about these highly crosslinked, insoluble, polymer networks. 

Overview of Multiple-Pulse Solid-State NMR Imaging Studies... 

One of the important applications of butylcalix[4]arenes arises from their ability to trap alkali metal ions. In particular, Cs+-calixarene complexes have received much attention because of the need to remove the Cs radionucleotide from nuclear wastes. Benevelli et al. have used one-pulse solid state NMR experiments to directly observe Li, Na and Cs ions in the host cavity [52]. More advanced experiments, which allow the investigation of metal lattice interactions were also reported. Rotational-echo double resonance (REDOR) NMR is a useful tool for obtaining structural details of butylcalix[4]arene [53]. Gullion and coworkers used REDOR to determine the position of the... 

These limitations have recently been eliminated using solid-state sources of femtosecond pulses. Most of the femtosecond dye laser teclmology that was in wide use in the late 1980s [11] has been rendered obsolete by tliree teclmical developments the self-mode-locked Ti-sapphire oscillator [23, 24, 25, 26 and 27], the chirped-pulse, solid-state amplifier (CPA) [28, 29, 30 and 31], and the non-collinearly pumped optical parametric amplifier (OPA) [32, 33 and 34]- Moreover, although a number of investigators still construct home-built systems with narrowly chosen capabilities, it is now possible to obtain versatile, nearly state-of-the-art apparatus of the type described below Ifom commercial sources. Just as home-built NMR spectrometers capable of multidimensional or solid-state spectroscopies were still being home built in the late 1970s and now are almost exclusively based on commercially prepared apparatus, it is reasonable to expect that ultrafast spectroscopy in the next decade will be conducted almost exclusively with apparatus ifom conmiercial sources based around entirely solid-state systems. 

Fig. 9. Solid-state NMR spectra of stiff chain aromatic polyesters containing sulfur bonds and tentative assignements of their signals, 401. A contact time of 2 ms and a pulse repetition time of 10 s were used...

In addition to sample rotation, a particular solid state NMR experiment is further characterized by the pulse sequence used. As in solution NMR, a multitude of such sequences exist for solids many exploit through-space dipolar couplings for either signal enhancement, spectral assignment, interauclear distance determination or full correlation of the spectra of different nuclei. The most commonly applied solid state NMR experiments are concerned with the measurement of spectra in which intensities relate to the numbers of spins in different environments and the resonance frequencies are dominated by isotropic chemical shifts, much like NMR spectra of solutions. Even so, there is considerable room for useful elaboration the observed signal may be obtained by direct excitation, cross polarization from other nuclei or other means, and irradiation may be applied during observation or in echo periods prior to... 

Using the OPENCORE NMR spectrometer, standard solid-state NMR experiments have been demonstrated in Ref. 2. They include 1H-13C CPMAS with TPPM decoupling, 13C-15N dipolar recoupling under MAS, 1H FSLG, 13C-13C 2D exchange, and so on. Here we show two more examples, where the spectrometer was used to implement standard pulse sequences, but in somewhat demanding circumstances in terms of sensitivity. 

The spectrometer supports phase cycling, asynchronous sequence implementation, and parameter-array experiments. Thus, most standard solid-state NMR experiments are feasible, including CPMAS, multiple-pulse H decoupling such as TPPM, 2D experiments, multiple-quantum NMR, and so on. In addition, the focus of development is on its extension of, or modification to, the hardware and/or the software, in the spirit of enabling the users to put their own new ideas into practice. In this paper, several examples of such have been described. They include the compact NMR and MRI systems, active compensation of RF pulse transients, implementation of a network analyzer, dynamic receiver-gain increment,31 and so on. 

It is clear that pulse sequences may not only be designed by analytical means, they may also be designed numerically (see, e.g., reviews on numerical aspects of solid-state NMR in [54, 65, 66]) using standard nonlinear optimization to well-defined analytical expressions [67, 68], by optimizing pulse sequences directly on the spectrometer [69], or by optimal control procedures [70-72] to name but a few of the possibilities. We will in this review restrict ourselves to optimal control design procedures that recently in analytical and numerical form have formed a new basis for efficient NMR experiment design. 

Magnetization transfer via proton-driven-spin-diffusion (PDSD) in MAS NMR is not by any means a new experiment. It was introduced in the early 1980s by Maciel and coworkers [136] and later used, described, and analyzed by numerous groups in relation to, e.g., biological solid-state NMR. In its original form, the experiment consists of a couple of oppositely phase n/2 pulses bringing the low-y... 

We note that optimal control is a universal tool for experiment design and has also, in solid-state NMR spectroscopy, found additional applications in the design of homonu-clear dipolar recoupling [41], broadband rf pulses and quantum gates [71], building blocks of symmetry-based recoupling experiments [129], quadrupolar multiple-quantum MAS experiments [165], and improved pulses for quadrupolar nuclei [166]. Numerous references to further applications with regard to liquid-state NMR can be found in [72]. 

The majority of double-resonance solid-state NMR experiments involving spin-1/2 nuclei use transfer of nuclear polarization via dipolar cross polarization (CP) to enhance polarization of the diluted spins S with small gyromagnetic ratio ys and significant longitudinal relaxation time T at the expense of abundant spins I with large y, and short 7 [215]. Typically, CP is used in combination with MAS, to eliminate the line broadening due to CS A, as well as with heteronuclear decoupling. To achieve the / S CP transfer, a (n/2)y pulse is applied at the I spin frequency,... 

Throughout the cross-polarization pulse sequence, a number of competing relaxation processes are occurring simultaneously. The recognition and understanding of these relaxation processes are critical in order to apply CP pulse sequences for quantitative solid state NMR data acquisition or ascertaining molecular motions occurring in the solid state. 

Fig. 9 Examples of simplifying solid state NMR spectra by the TOSS and delayed decoupling pulse sequences. Shown is a comparison of the 31P CP/MAS NMR spectrum of fosinopril sodium utilizing the standard pulse sequence (A) and the TOSS routine (B). Also shown is the full 13C CP/MAS NMR spectrum of fosinopril sodium (C) and the nonprotonated carbon spectrum (D) obtained from the delayed decoupling pulse sequence utilizing a 80 /us delay time. Signals due to the methyl carbon resonances (0-30 ppm) are not completely eliminated due to the rapid methyl group rotation, which reduces the carbon-proton dipolar couplings.

Within various pharmaceutical laboratories (industrial and academic), the mul-tinuclear technique of solid state NMR has primarily been applied to the study of polymorphism at the qualitative and quantitative levels. Although the technique ideally lends itself to the structure determination of drug compounds in the solid state, it is anticipated that in the future, solid state NMR will become routinely used for method development and problem solving activities in the analytical/materials science/physical pharmacy area of the pharmaceutical sciences. During the past few years, an increasing number of publications have emerged in which solid state NMR has become an invaluable technique. With the continuing development of solid state NMR pulse sequences and hardware improvements (increased sensitivity), solid state NMR will provide a wealth of information for the physical characterization of pharmaceutical solids. 

---