Sensitivity Gains, Linearity, and Spectral Reproducibility in Nonuniformly Sampled Multidimensional MAS NMR Spectra of High Dynamic Range

Recently, we have demonstrated that considerable inherent sensitivity gains are attained in MAS NMR spectra acquired by nonuniform sampling (NUS) and introduced maximum entropy interpolation (MINT) processing that assures the linearity of transformation between the time and frequency domains. In this report, we examine the utility of the NUS/MINT approach in multidimensional datasets possessing high dynamic range, such as homonuclear C-13-C-13 correlation spectra. We demonstrate on model compounds and on 1-73-(U-C-13,N-15)/74-108-(U-N-15) E. coli thioredoxin reassembly, that with appropriately constructed 50 % NUS schedules inherent sensitivity gains of 1.7-2.1-fold are readily reached in such datasets. We show that both linearity and line width are retained under these experimental conditions throughout the entire dynamic range of the signals. Furthermore, we demonstrate that the reproducibility of the peak intensities is excellent in the NUS/MINT approach when experiments are repeated multiple times and identical experimental and processing conditions are employed. Finally, we discuss the principles for design and implementation of random exponentially biased NUS sampling schedules for homonuclear C-13-C-13 MAS correlation experiments that yield high-quality artifact-free datasets.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (13C, 15N, 18O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)7, in both 2– 8 GHz and 6–18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to pro- vide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues (H218O and HDO), and a least-squares rm(1) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O–O equilibrium distances at the 0.01 Å level.

Broadband Fourier transform rotational spectroscopy for structure determination: The water heptamer

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have changed the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (C-13, N-15, O-18) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2-8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water heptamer, (H2O)(7), in both 2-8 GHz and 6-18 GHz frequency ranges. Two isomers of the water heptamer have been observed in a pulsed supersonic molecular expansion. High level ab initio structural searches were performed to provide plausible low-energy candidates which were directly compared with accurate structures provided from broadband rotational spectra. The full substitution structure of the most stable species has been obtained through the analysis of all possible singly-substituted isotopologues ((H2O)-O-18 and HDO), and a least-squares r(m)((1)) geometry of the oxygen framework determined from 16 different isotopic species compares with the calculated O-O equilibrium distances at the 0.01 angstrom level. (C) 2013 Elsevier B.V. All rights reserved.

Investigating the Effects of Various Crowd Characteristics on the Dynamic Properties of an Occupied Structure

One of the challenges for structural engineers during design is considering how the structure will respond to crowd-induced dynamic loading. It has been shown that human occupants of a structure do not simply add mass to the system when considering the overall dynamic response of the system, but interact with it and may induce changes of the dynamic properties from those of the empty structure. This study presents an investigation into the human-structure interaction based on several crowd characteristics and their effect on the dynamic properties of an empty structure. The dynamic properties including frequency, damping, and mode shapes were estimated for a single test structure by means of experimental modal analysis techniques. The same techniques were utilized to estimate the dynamic properties when the test structure was occupied by a crowd with different combinations of size, posture, and distribution. The goal of this study is to isolate the occupant characteristics in order to determine the significance of each to be considered when designing new structures to avoid crowd serviceability issues. The results are presented and summarized based on the level of influence of each characteristic. The posture that produces the most significant effects based on the scope of this research is standing with bent knees with a maximum decrease in frequency of the first mode of the empty structure by 32 percent atthe highest mass ratio. The associated damping also increased 36 times the damping of the empty structure. In addition to the analysis of the experimental data, finite element models and a two degree-of-freedom model were created. These models were used to gain an understanding of the test structure, model a crowd as an equivalent mass, and also to develop a single degree-of-freedom (SDOF) model to best represent a crowd of occupants based on the experimental results. The SDOF models created had an averagefrequency of 5.0 Hz, within the range presented in existing biomechanics research, and combined SDOF systems of the test structure and crowd were able to reproduce the frequency and damping ratios associated with experimental tests. Results of this study confirmed the existence of human-structure interaction andthe inability to simply model a crowd as only additional mass. The two degree-offreedom model determined was able to predict the change in natural frequency and damping ratio for a structure occupied by multiple group sizes in a single posture. These results and model are the preliminary steps in the development of an appropriate methodfor modeling a crowd in combination with a more complex FE model of the empty structure.