Notes: To date, both the intermolecular multiple-quantum coherence (MQC) and demagnetizing field models have led to fully quantitative predictions of NMR signals in a highly polarized system using the CRAZED and similar sequences. In this paper, measurements of apparent MQC diffusion rates, Dnapp, for a specific apparent coherence order, n, were used to investigate the equivalent between the intermolecular MQC and demagnetizing field treatments. A number of physical effects were analyzed both theoretically and experimentally. These effects include molecular diffusion, variation in dipolar correlation distance, radiation damping, inhomogeneous broadening, and spin relaxation, all of which may alter the NMR signal. Two variations of a two-pulse CRAZED sequence, where the signal attenuation is almost entirely caused by the diffusion weighting, were designed to accurately measure and characterize Dnapp during the evolution period. Apparent diffusion rates were extracted from a least-squares fitting of a series of 1H spectra, measured with varying diffusion weighting factors. Complete theoretical formations were explicitly derived from both the intermolecular MQC and demagnetizing field treatments. Numerical simulations based on the demagnetizing field treatment were performed and it was found that the model can be used to predict the apparent diffusion rates. A novel diffusion model for intermolecular MQC is proposed in which the phase shift of each individual spin on different molecules is considered to be uncorrelated. This model successfully predicts the unconventional diffusion behaviors of intermolecular MQCs, specifically for differences of apparent diffusion rates between inter- and intramolecular MQCs. Our theoretical predictions and experimental confirmation demonstrate, for the first time, that Dnapp for intermolecular MQCs of order n are characterized by Dnapp=nDT for n≥2 and D0app=2DT for n=0, where DT is the translational molecular diffusion rate of the single quantum coherences. These results do not coincide with Dn=n2DT for n≥0 which is a general relationship for an intramolecular n-quantum coherence. These works about the apparent diffusion rates during the evolution period of the CRAZED sequences provide additional evidence to support the argument of the equivalence between the intermolecular MQC and demagnetizing field models. The general results derived from both intermolecular MQC and demagnetizing field treatments in this report can reasonably explain new observations of diffusion phenomena in nonlinear spin echoes by Kimmich and co-workers. Even though the theoretical prediction about intermolecular MQC diffusion is verified only with specific experiments using tailor-made pulse sequences, it is demonstrated that the function dependence of diffusion rate on coherence order is general. These results provide independent evidence to support the intermolecular MQC theory proposed by Warren and co-workers. © 2001 American Institute of Physics.

Notes: Liquid nuclear magnetic resonance behaviors related to intermolecular dipolar interactions were investigated theoretically and experimentally in highly polarized two-component spin systems. A modified CRAZED pulse sequence was designed to investigate relative signal intensities with considerations of spin transverse relaxation, longitudinal relaxation, molecular diffusion, and optimal radio-frequency flip angles. The dissipation of the demagnetizing field due to relaxation and diffusion processes during the detection period was taken into account as well. For the first time, vigorous analytical expressions of the spin dynamics, including all the effects mentioned above, were derived from the combination of the demagnetizing field model and product operator formalism. In the regime where the linear approximation (γμ0M0t(very-much-less-than)1) is valid, these explicit analytical expressions can quantitatively describe the signal behaviors related to intermolecular dipolar interactions. All the theoretical predictions based on the analytical expressions for the directly excited component are in excellent agreement with experimental observations reported previously. Several valuable insights for the indirectly excited component were gained from the analytical expressions and verified by experimental measurements, including optimal radio-frequency flip angles, unusual relative signal intensities for n=−2 and n=2, and unconventional diffusion and multi-exponential longitudinal relaxation processes, where n is the ratio of the coherence-selection gradient areas in the CRAZED pulse sequence. In addition, n-order diffusion coefficients of the directly and indirectly excited spins during the evolution period predicted by the demagnetizing field picture are found to be the same as those obtained with the combination of the intermolecular multiple-quantum picture and Gaussian phase distribution approximation which is valid in the case of unrestricted isotropic diffusion. These results suggest that a combination of the demagnetizing field model and product operator formalism provides excellent predictive power and computational convenience for diffusion and relaxation behaviors in two-component systems. These quantitative studies may also provide an opportunity to probe specific sources of new contrast for medical MR imaging. © 2001 American Institute of Physics.

Notes: A novel Monte Carlo technique, the rebridging configurational-bias (RCB) method, has been developed to rearrange inner sections of chain molecules having strong intramolecular interactions along the backbone. The ability of sampling inner chain segments is important for the simulation of systems with low concentration of chain ends, such as polymers and molecules with cyclic structures. In the RCB method, inner segments are removed and then regrown site-by-site in a configurational-bias fashion. However, a short preliminary simulation is carried out to calculate weighting functions based on histograms of the separation distance between pairs of sites along the chain; these functions are used to bias the trial positions of growing inner sites so as to promote efficient chain closure. A look-ahead search scheme is employed for the sampling of the last two sites to increase the overall acceptance rate of the reconstruction process. The validity and performance of the new algorithm were tested by studying linear alkane systems of various chain lengths. Fast conformational equilibration was observed, from the level of local bond orientations to the level of the chain end-to-end vector orientations. Cyclic alkanes containing from 8 to 100 carbon atoms were also studied by using the RCB method. Our results for the conformational properties of cyclooctane are generally consistent with previous molecular dynamics (MD) results and with experimental data. The vapor–liquid coexistence curve of cyclooctane was also mapped out by using the RCB method in conjunction with a histogram reweighting technique for the analysis of isothermal–isobaric simulations. © 2000 American Institute of Physics.

Notes: Grasses with the C3 photosynthetic pathway are commonly considered to be more nutritious host plants than C4 grasses, but the nutritional quality of C3 grasses is also more greatly impacted by elevated atmospheric CO2 than is that of C4 grasses; C3 grasses produce greater amounts of nonstructural carbohydrates and have greater declines in their nitrogen content than do C4 grasses under elevated CO2. Will C3 grasses remain nutritionally superior to C4 grasses under elevated CO2 levels? We addressed this question by determining whether levels of protein in C3 grasses decline to similar levels as in C4 grasses, and whether total carbohydrate : protein ratios become similar in C3 and C4 grasses under elevated CO2. In addition, we tested the hypothesis that, among the nonstructural carbohydrates in C3 grasses, levels of fructan respond most strongly to elevated CO2. Five C3 and five C4 grass species were grown from seed in outdoor open-top chambers at ambient (370 ppm) or elevated (740 ppm) CO2 for 2 months. As expected, a significant increase in sugars, starch and fructan in the C3 grasses under elevated CO2 was associated with a significant reduction in their protein levels, while protein levels in most C4 grasses were little affected by elevated CO2. However, this differential response of the two types of grasses was insufficient to reduce protein in C3 grasses to the levels in C4 grasses. Although levels of fructan in the C3 grasses tripled under elevated CO2, the amounts produced remained relatively low, both in absolute terms and as a fraction of the total nonstructural carbohydrates in the C3 grasses. We conclude that C3 grasses will generally remain more nutritious than C4 grasses at elevated CO2 concentrations, having higher levels of protein, nonstructural carbohydrates, and water, but lower levels of fiber and toughness, and lower total carbohydrate : protein ratios than C4 grasses.

Notes: [Auszug] To identify changes in gene expression associated with tumor progression and metastasis in vivo, we investigated differential gene expression in a metastatic squamous carcinoma model established in syngeneic mice, including a tumorigenic line PAM 212, and metastatic sublines derived from PAM 212 ...

Notes: The title compound, C18H12N4O·H2O, adopts the keto tautomeric form and the azomethine C=N double bond is in the E configuration. The dihedral angle between the planes of the diazafluorene moiety and the phenyl ring is 11.3 (1)°. In the solid state, the molecules form infinite chain-like structures via O—H...N hydrogen bonds involving the water molecules and diazafluorene moieties.