Determination of polymer crystallinity by the multivariable curve resolution method in 13C solid NMR spectrum.

Most of the polymers are composed of a crystal part, an amorphous part, and a transitional interfacial part. These components present disparate physical and chemical characteristics. However, it always suffers from peak overlapping in solid NMR spectrum in order to acquire polymer's crystallinity. The polyethylene oxide (PEO) sample was tested using the Torchia pulse sequence combined with the Multivariate Curve Resolution (MCR) method. A two dimensional CP/MAS spectrum containing spin-lattice relaxation time (T1) information was acquired. After the correction based on the reciprocity relation, the overlapped peaks were resolved and quantified together with their T1's. Crystallinity is therefore observed naturally according to components' content ratios associated with their T1 values.

Selective excitation with asymmetric adiabatic pulses for NMR spectroscopy.

Existing selective pulses are mainly constructed in the forms of classically shaped pulses, such as the Gaussian pulses, or generated by using numerical optimization methods. However, all of these pulses are highly sensitive to radiofrequency (RF) intensity variation, which means their performance is highly dependent on the accuracy and stability of the RF intensity. Even a slight RF intensity deviation can cause severe degradation in the excitation profile. To solve this problem, we propose a method for narrow selective excitation by sequential application of a pair of phase-opposite asymmetric adiabatic pulses, all within two scans. By retaining the adiabatic character, the new method is highly robust to RF intensity variation. Moreover, it has flexible excitation bandwidth, ranging from line-selective to narrow-band-selective pulses. The method is tested both in numerical simulations and solution-state NMR experiments.

Decoding the individual finger movements from single-trial functional magnetic resonance imaging recordings of human brain activity.

Multivariate pattern classification analysis (MVPA) has been applied to functional magnetic resonance imaging (fMRI) data to decode brain states from spatially distributed activation patterns. Decoding upper limb movements from non-invasively recorded human brain activation is crucial for implementing a brain-machine interface that directly harnesses an individual's thoughts to control external devices or computers. The aim of this study was to decode the individual finger movements from fMRI single-trial data. Thirteen healthy human subjects participated in a visually cued delayed finger movement task, and only one slight button press was performed in each trial. Using MVPA, the decoding accuracy (DA) was computed separately for the different motor-related regions of interest. For the construction of feature vectors, the feature vectors from two successive volumes in the image series for a trial were concatenated. With these spatial-temporal feature vectors, we obtained a 63.1% average DA (84.7% for the best subject) for the contralateral primary somatosensory cortex and a 46.0% average DA (71.0% for the best subject) for the contralateral primary motor cortex; both of these values were significantly above the chance level (20%). In addition, we implemented searchlight MVPA to search for informative regions in an unbiased manner across the whole brain. Furthermore, by applying searchlight MVPA to each volume of a trial, we visually demonstrated the information for decoding, both spatially and temporally. The results suggest that the non-invasive fMRI technique may provide informative features for decoding individual finger movements and the potential of developing an fMRI-based brain-machine interface for finger movement.

Trust-region algorithm for the inversion of molecular diffusion NMR data.

Diffusion NMR experiments are very useful in studying structural and dynamical properties of molecules and in sorting out components from mixtures. A number of numerical approaches have been developed for the processing of diffusion NMR data. In this paper, numerical problems of the direct regularization methods such as CONTIN, MaxEnt, and the newly proposed ITAMeD approach are illustrated by analyzing simulated and experimental data. It allows us to further develop a new method to calculate the distribution of diffusion coefficients. Therefore, we present here an iterative regularization method based on the Trust-Region Algorithm for the Inversion (TRAIn) of molecular diffusion NMR data. It is demonstrated in this paper that our approach overcomes major numerical difficulties of the direct regularization methods mentioned above. Besides, this method reconstructs more reliable diffusion coefficient distributions, especially for real world samples of which the diffusion coefficients are nonsymmetrically distributed.

Diffusion of water inside carbon nanotubes studied by pulsed field gradient NMR spectroscopy.

Diffusion dynamics of guest molecules in nanopores has been studied intensively because diffusion is center on a number of research fields such as separation, drug delivery, chemical reactions, and sensing. In the present work, we report an experimental investigation of the self-diffusion of water inside carbon nanotube (CNT) channels using a pulsed field gradient (PFG) NMR method. The dispersion of CNTs homogeneously in water and cooling to temperatures below the melting point of bulk water allow us to probe the translational motion of confined water molecules. The results demonstrate that the self-diffusion coefficient of water in CNTs is highly dependent on the diffusion time and CNT diameter. In particular, the diffusivity of water in double-walled carbon nanotubes (DWNTs) with an average inner diameter of 2.3 ± 0.3 nm is twice that in multiwalled carbon nanotubes (MWNTs) with an average inner diameter of 6.7 ± 0.8 nm in the temperature range of 263-223 K. In addition, the effective self-diffusion coefficient in DWNTs is 1 order of magnitude higher than that reported for mesoporous silica materials with a similar pore size. The faster diffusivity of water in CNTs could be attributed to the ordered hydrogen bonds formed between water molecules within the confined channels of CNTs and the weak interaction between water and the CNT walls.

Quantitative structural characterization of POSS and octavinyl-POSS nanocomposites by solid state NMR.

The ratio between two different (29)Si atoms in chloromethylphenyl isobutyl Polyhedral Oligomeric Silsesquioxane (POSS) was determined based on the quantitative cross polarization (QCP) (Shu et al., Chem. Phys. Lett. 462 (2008) 125) in solid-state NMR. For a (29)Si/(1)H spin system, cross polarization and depolarization together with the reciprocity relation were performed with optimized experimental conditions. It saves considerable experimental time compared to the (29)Si direct polarization experiment. The same method was further applied to octavinyl-POSS nanocomposites containing perfluoropolyether (PFPE) for deriving directly and accurately the average numbers of reacted vinyl groups, which may not be obtained by combining FTIR and solution (1)H NMR. In principle, the aforementioned method proves to be valuable in quantitative characterization of silicon related structures in bulk materials.

Triterpenoid saponins from the fruits of Aesculus pavia.

The compounds, named aesculiosides Ia-Ie, IIa-IId, and IVa-IVc, were isolated from an ethanol extract of the fruits of North American Aesculus pavia, along with two known compounds. Their structures were characterized as polyhydroxyoleanene pentacyclic triterpenoid saponins by spectroscopic and chemical analyses. These saponins were divided into three elution zones by chromatography according to the polarity because of the acyl substitution at C-21 and C-22 of the aglycone saponins moiety. These are structurally different from those isolated from Eurasian Aesculus hippocastanum and Aesculus chinensis in their oligosaccharide moieties.

Systematic bias in NMR diffusion measurements on polydisperse systems.

Least-squares fitting of the Stejskal-Tanner equation is a routine process in the measurement of molecular diffusion coefficient (MDC) using Nuclear Magnetic Resonance (NMR) Spectroscopy. It is simple and elegant. However, a bias of the MDC is noticed when the system is polydispersed. This is due to improper accounts of the diffusion coefficient distribution. Eventually, it leads to a discrepancy between the observed MDC and the statistical mean value of the distribution. To reveal the discrepancy, an analytical solution is derived when the diffusion data is taken a logarithmic linearization. Computer simulation is also applied to obtain a non-linear regression result. For a Gaussian distribution of the MDCs, the bias is proportional to the square of the distribution width (linear regression), but it is also inversely proportional to the statistical mean value of the distribution (non-linear regression). This indicates that the MDC derived from Stejskal-Tanner equation only holds well for narrow distribution of MDCs. Otherwise, molecular radius derived from the Stokes-Einstein equation needs to be reconsidered due to the incorrect estimation of the MDC.

Analytical solution of cross polarization dynamics.

The first analytical solution under Hartman-Hahn match (ω1I=ω1S) for a stationary sample was derived by Müller et al. After the introduction of magic angle spinning (MAS), the dynamics becomes much more complicated. By transferring the Hamiltonian into a rotating frame, Stejskal et al. derived the effective Hamiltonian and the new condition of Hartman-Hahn match (ω1I-ω1S=nωr,n=±1,±2), which leads to an analytical solution of CP dynamics under very fast MAS. For both stationary and fast MAS results, the effective Hamiltonians are time-independent in the rotating frame. Under Hartman-Hahn match (ω1I=ω1S) and arbitrary MAS speed condition, the Hamiltonian is no longer time-independent, making the CP dynamics very intriguing. In this work, the solution is derived analytically in the zero- and double-quantum spaces. The initial polarization in the double-quantum space is a constant of motion under strong pulse condition (|ω1I+ω1S|≫|d(t)|), while the Hamiltonian in the zero-quantum space reduces to d(t)σz(Δ), which is time dependent but self commuting all the time. This Hamilontian acts on the initial density matrix successively, leading to an analytical solution of CP dynamics. Based on the result, a phenomenological solution is derived. When the MAS speed ωr→0 , this solution reduces to Müller's formula except a spin-lattice relaxation time in the rotating frame (T1ρ). Computer simulations and experimental results agree well with the solutions.

Coherent excitation with phase-incremented pulses.

An outline is given for calculating the evolution of a spin system by a pulse sequence with phase-incremented pulses (PIPs). It is done in a frame with a speed of 2pideltaf=deltaphi/deltatau relative to the rotating frame, where deltaphi and deltatau are the phase- and time-increment of the PIP. This particular frame is defined as the eigenframe, in which the phase of the PIP for the center band is stationary and is subjected to a universal phase shift (UPS=-deltaphi/2), and the strength of the PIP is scaled by a factor of lambda=2[1-cos(deltaphi)]/(deltaphi). The phase differences between different eigenframes can be attributed to the initial phases of the PIPs, making it possible to use the Bloch vector model even in different eigenframes. A new way is provided to construct composite pulses with not only amplitude and phase modulations but also offset modulation. Several examples, including a broadband inversion pulse, a Hahn spin echo, and a selective inversion and null pulse, all composed of PIPs, are discussed in detail.

Ringing effects eliminated spin echo in solids.

Two types of ringing effects eliminated spin echo sequences have been introduced. To achieve the task, two additional 90° pulses with proper phase cycles are placed at the beginning of the pulse sequences. The spin echo time is calculated with the perturbation method to the first order, i.e. taking into account only the dipolar secular term. The non-secular term causes an imaginary part of the FID, leading to an unsymmetrical NMR spectrum. This effect, according to a symmetry of NMR sequences under phase inversion, can be compensated by inverting all the x and -x or y and -y phases. The properties of the symmetry are derived based on the theory of density matrix. In addition, the non-secular term also results in a small drop (several per cent) of the echo amplitude, but it nearly does not affect the echo time. With these pulse sequences we are able to get a spectrum with an echo delay only 1.1µs without distortion using a Bruker AVANCE III NMR instrument.

Pivotal steps towards quantification of molecular diffusion coefficients by NMR.

Using nuclear magnetic resonance (NMR) spectroscopy with a pair of pulsed field gradients (PFGs), Stajeskal and Tanner successfully measured molecular diffusion coefficients in solution in 1965. This method has since been used extensively in various applications, especially after the PFG was implemented in commercial NMR probes. Due to the nonuniformity of the PFG and radio frequency (RF) fields, molecules distributed throughout the sample experience different PFG and RF fields and contribute unevenly to the measured diffusion coefficients, resulting in considerable errors in conventional NMR diffusion experiments. By selective excitation of a central sample region with an offset-independent adiabatic inversion pulse and a PFG, a uniform RF field can be assumed, and the PFG can be represented as a linear approximation. Under these conditions, the molecules diffuse as if they were all experiencing the same effective gradient g(e), leading to a Gaussian signal decay as a function of the PFG strength. Quantitative measurement of molecular diffusion coefficients is therefore made possible. From the diffusion coefficient of a 90 % H(2)O/10 % D(2)O sample, it is convenient to calibrate g(e) with a Java program. In a similar way the nonlinearity of the PFG can be corrected.

Quantitative measurement of molecular diffusion coefficients by NMR spectroscopy.

An offset-independent adiabatic inversion pulse is used in the diffusion experiment to uniformly excite a sample region that is sufficiently long to ignore the ending effects, yet is short enough to have a homogeneous RF field and to represent the pulsed field gradient with a linear approximation. Under these conditions, the diffusion decay of the peak intensity appears to be Gaussian as a function of the effective gradient field ge as if all the molecules inside the selected region experienced the same ge. Quantitative measurement of molecular diffusion coefficients is therefore made possible.

Six new triterpenoid saponins from the root and stem bark of Cephalanthus occidentalis.

From the root and stem bark of Cephalanthus occidentalis L., a common American wetland species, six new triterpenoid saponins (1 - 6), together with 29 known compounds were isolated and identified. On the basis of spectroscopic analysis and chemical degradation, the structures of new compounds were elucidated as 3-O-beta-glucopyranosylcincholic acid (1), cincholic acid 28-O-beta-glucopyranosyl ester (2), 3-O-beta-glucopyranosyl-(1-->4)-beta-fucopyranosylcincholic acid (3), 3-O-beta-glucopyranosyl-(1-->4)-beta-fucopyranosylcincholic acid 28-O-beta-glucopyranosyl ester (4), 3-O-beta-glucopyranosylcincholic acid 28-O-alpha-arabinopyranosyl-(1-->2)-beta-glucopyranosyl ester (5), and 3-O-beta-glucopyranosylquinovic acid 28-O-alpha-arabinopyranosyl-(1-->2)-beta-glucopyranosyl ester (6).

Near neighbor approximation in nuclear magnetic resonance.

A new way to deal with the excitation by multiple effective RF fields with interference is presented using the coherent averaging theory. It significantly simplifies the calculation of the effect of RF interference that occurs in the excitations by periodic pulses and phase-incremented pulses (PIPs). This approach shows that each neighboring RF field contributes to an excitation profile an offset shift, which is termed the Bloch-Siegert offset shift (BSOS). The BSOS depends not only on the strengths of both RF fields that interfere with each other but also on their relative phase between the two RF fields. Consequently, it can be positive, negative, and zero. In addition, the BSOS is also inversely proportional to the frequency separation of the two RF fields. Therefore, only a few near neighbors need to be taken into account in most cases, resulting in a near neighbor approximation (NNA). The BSOS for two multiband excitation profiles, one by a periodic pulse and the other by a PIP, are calculated using the NNA. The results are in good agreement with the computer simulated ones.

New camptothecin and ellagic acid analogues from the root bark of Camptotheca acuminata.

As part of a study on chemical constituents of Camptotheca species, one new natural camptothecin analogue (2), two new alkaloids (3, 4), one new ellagic acid analogue (5), and 19 known compounds (1, 6-23) have been isolated from the root bark, stem bark, fruits, and leaves of Camptotheca acuminata Decaisne. The structures of 2-5 were determined from spectral data to be 10-methoxy-20-O-acetylcamptothecin (2), 20-O-beta-glucopyranosyl 18-hydroxycamptothecin (3), 20-formylbenz indolizino [1,2-b]quino-line-11(13H)-one (4), and 3,4-methylenedioxy-3'-O-methyl-5'-hydroxyellagic acid (5).