The complete iodine and nitrogen nuclear electric quadrupole coupling tensors for fluoroiodoacetonitrile determined by chirped pulse Fourier transform microwave spectroscopy

from Journal of Chemical Physics: All Topics

G. S. Grubbs, II, G. Kadiwar, W. C. Bailey, and S. A. Cooke

Molecular pulsed jet, chirped-pulse Fourier transform microwave spectroscopy has been used to record 499 transitions for the title molecule. Measurements have been made in the 8–16 GHz regions. Vibrational and electronic ground state rotational constants A, B, and C have been obtained, together with centrifugal distortion terms. The complete iodine and nitrogen nuclear quadrupole coupling tensors have been determined for the first time. Quantum chemical calculations have been performed to aid with analyses and, in particular, to aid in determining the signs of the off-diagonal components of the nuclear quadrupole coupling tensors. An experimentally determined relative electronegativity scale for several polyhalomethyl groups is proposed.

An NMR study of macromolecular aggregation in a model polymer-surfactant solution

from Journal of Chemical Physics: All Topics

Suliman Barhoum and Anand Yethiraj

A model complex-forming nonionic polymer–anionic surfactant system in aqueous solution has been studied at different surfactant concentrations. Using pulsed-field-gradient diffusion NMR spectroscopy, we obtain the self-diffusion coefficients of poly(ethylene glycol) (PEO) and sodium dodecyl sulfate (SDS) simultaneously and as a function of SDS concentration. In addition, we obtain NMR relaxation rates and chemical shifts as a function of SDS concentration. Within the context of a simple model, our experimental results yield the onset of aggregation of SDS on PEO chains (CAC=3.5 mM), a crossover concentration (C₂=60 mM) which signals a sharp change in relaxation behavior, as well as an increase in free surfactant concentration and a critical concentration (C_m=145 mM) which signals a distinct change in diffusion behavior and a crossover to a solution containing free micelles. C_m also marks the concentration above which obstruction effects are definitely important. In addition, we obtain the concentration of SDS in monomeric form and in the form of free micelles, as well as the average number of SDS molecules in a PEO-SDS aggregate (N_Aggr). Taken together, our results suggests continuous changes in the aggregation phenomenon over much of the concentration but with three distinct concentrations that signal changes in the nature of the aggregates.

Communications: Nanomagnetic shielding: High-resolution NMR in carbon allotropes

Y. Kim,¹ E. Abou-Hamad,² A. Rubio,³ T. Wågberg,⁴ A. V. Talyzin,⁴ D. Boesch,⁵ S. Aloni,⁵ A. Zettl,⁵ D. E. Luzzi,^1,6 and C. Goze-Bac²

The understanding and control of the magnetic properties of carbon-based materials is of fundamental relevance in applications in nano- and biosciences. Ring currents do play a basic role in those systems. In particular the inner cavities of nanotubes offer an ideal environment to investigate the magnetism of synthetic materials at the nanoscale. Here, by means of ¹³C high resolution NMR of encapsulated molecules in peapod hybrid materials, we report the largest diamagnetic shifts (down to −68.3 ppm) ever observed in carbon allotropes, which is connected to the enhancement of the aromaticity of the nanotube envelope upon doping. This diamagnetic shift can be externally controlled by in situ modifications such as doping or electrostatic charging. Moreover, defects such as C-vacancies, pentagons, and chemical functionalization of the outer nanotube quench this diamagnetic effect and restore NMR signatures to slightly paramagnetic shifts compared to nonencapsulated molecules. The magnetic interactions reported here are robust phenomena independent of temperature and proportional to the applied magnetic field. The magnitude, tunability, and stability of the magnetic effects make the peapod nanomaterials potentially valuable for nanomagnetic shielding in nanoelectronics and nanobiomedical engineering.

Detecting diffusion-diffraction patterns in size distribution phantoms using double-pulsed field gradient NMR: Theory and experiments

from Journal of Chemical Physics: All Topics

Noam Shemesh, Evren Ozarslan, Peter J. Basser, and Yoram Cohen

NMR observable nuclei undergoing restricted diffusion within confining pores are important reporters for microstructural features of porous media including, inter-alia, biological tissues, emulsions and rocks. Diffusion NMR, and especially the single-pulsed field gradient (s-PFG) methodology, is one of the most important noninvasive tools for studying such opaque samples, enabling extraction of important microstructural information from diffusion-diffraction phenomena. However, when the pores are not monodisperse and are characterized by a size distribution, the diffusion-diffraction patterns disappear from the signal decay, and the relevant microstructural information is mostly lost. A recent theoretical study predicted that the diffusion-diffraction patterns in double-PFG (d-PFG) experiments have unique characteristics, such as zero-crossings, that make them more robust with respect to size distributions. In this study, we theoretically compared the signal decay arising from diffusion in isolated cylindrical pores characterized by lognormal size distributions in both s-PFG and d-PFG methodologies using a recently presented general framework for treating diffusion in NMR experiments. We showed the gradual loss of diffusion-diffraction patterns in broadening size distributions in s-PFG and the robustness of the zero-crossings in d-PFG even for very large standard deviations of the size distribution. We then performed s-PFG and d-PFG experiments on well-controlled size distribution phantoms in which the ground-truth is well-known a priori. We showed that the microstructural information, as manifested in the diffusion-diffraction patterns, is lost in the s-PFG experiments, whereas in d-PFG experiments the zero-crossings of the signal persist from which relevant microstructural information can be extracted. This study provides a proof of concept that d-PFG may be useful in obtaining important microstructural features in samples characterized by size distributions.

Determination of outer-sphere dipolar time correlation functions from high-field NMR measurements. Example of a Gd complex in a viscous solvent

from Journal of Chemical Physics: All Topics

Pascal H. Fries, Daniel Imbert, and Andrea Melchior

We consider a diamagnetic species carrying a nuclear spin and having a purely outer-sphere dynamics with respect to a Gd³⁺ complex. The maximal structural and dynamic information attainable from the paramagnetic relaxation (rate) enhancement (PRE) of this nuclear spin due to the Gd³⁺ electronic spin is the outer-sphere dipolar time correlation function (OS-DTCF) of the relative position of these spins. We show how to determine this OS-DTCF by a model-free analysis of high-field PRE measurements, which accounts for the relative diffusion coefficient of the spin carrying species derived from pulsed-gradient spin-echo experiments. The method rests on the spectral characterization of the OS-DTCF through a PRE property, the “star” relaxivity, which can be measured over an unexpectedly large frequency range by combining multiple field and temperature NMR experiments. It is illustrated in the case of the ¹H spins on the three diamagnetic probes tert-butanol CHD₂(CD₃)₂COD and glycerol (CD₂OD)₂CHOD and CHDOD–CDOD–CD₂OD interacting with Gddtpa²⁻ (dtpa⁵⁻=diethylen triamin pentaacetate) in a viscous glycerol-d8/D₂O solvent. The general usefulness of the OS-DTCF for the description of the liquid state and electronic spin relaxation is discussed.