Prony methods in NMR spectroscopy

The Prony method and a modified Prony method (MPM), developed to improve the performance of this technique at low signal-to-noise ratio, are described and applied to analysis of magnetic resonance spectroscopy (MRS) signals. Furthermore, the way in which results from MPM can be used as prior information in a Bayesian model is also described. First, analysis on simulated data is used to establish the methods' limits of reliability. Their performance with respect to peak identification and quantification of nuclear magnetic resonance parameters are then assayed on real data. Results of application of the methods to ¹H-MRS signals from cultured cells are discussed and compared with those deriving from application of fast Fourier transform. © 1997 John Wiley & Sons, Inc. Int J Imaging Syst Technol, 8, 565–571, 1997     

Single-ensemble-based eigen-processing methods for color flow imaging--Part II. The matrix pencil estimator

Parametric spectral estimators can potentially be used to obtain flow estimates directly from raw slow-time ensembles whose clutter has not been suppressed. We present a new eigen-based parametric flow estimation method called the matrix pencil, whose principles are based on a matrix form under the same name. The presented method models the slow-time signal as a sum of dominant complex sinusoids in the slow-time ensemble, and it computes the principal Doppler frequencies by using a generalized eigen-value problem-formulation and matrix rank reduction principles. Both fixed rank (rank-one, rank-two) and adaptive-rank matrix pencil flow estimators are proposed, and their potential applicability to color flow signal processing is discussed. For the adaptive-rank estimator, the nominal rank was defined as the minimum eigen-structure rank that yields principal frequency estimates with a spread greater than a prescribed bandwidth. In our initial performance evaluation, the fixed-rank matrix pencil estimators were applied to raw color flow data (transmit frequency: 5 MHz; pulse repetition period: 0.175 ms; ensemble size: 14) acquired from a steady flow phantom (70 cm/s at centerline) that was surrounded by rigid-tissue-mimicking material. These fixed-rank estimators produced velocity maps that are well correlated with the theoretical flow profile (correlation coefficient: 0.964 to 0.975). To facilitate further evaluation, the matrix pencil estimators were applied to synthetic slow-time data (transmit frequency: 5 MHz; pulse repetition period: 1.0 ms; ensemble size: 10) modeling flow scenarios without and with tissue motion (up to 1 cm/s). The bias and root-mean-squared error of the estimators were computed as a function of blood-signal-to-noise ratio and blood velocity. The matrix pencil flow estimators showed that they are comparatively less biased than most of the existing frequency-based flow estimators like the lagone autocorrelator.     

Quantitative 1H NMR spectroscopy of blood plasma metabolites

The absolute quantification of blood plasma metabolites by proton NMR spectroscopy is complicated by the presence of a baseline and broad resonances originating from serum macromolecules and lipoproteins. A method for spectral simplification of proton NMR spectra of blood plasma is presented. Serum macromolecules and metabolites are completely separated by utilizing the large difference in translational diffusion coefficients in combination with diffusion-sensitized proton NMR spectroscopy. The concentration of blood plasma metabolites can be quantified by using formate as an internal concentration reference. The results are compared with those obtained with ultrafiltration, a traditional method for separating macromolecules and metabolites, and demonstrate an excellent correlation between the two methods. The general nature of diffusion-sensitized NMR spectroscopy allows application on a wide range of biological fluids.     

Quantitative determination of glucose in blood plasma and in fruit juices by combined WATR-CPMG 1H NMR spectroscopy.

The quantitative analysis of pure glucose solution < or = 225 mM (< or = 40.8 mg/mL) in 90/10 H2O/D2O was successfully completed in dilute aqueous solution by the WATR-CPMG method whereby the T2 of the water resonance is manipulated by the WATR method followed by elimination of the water peak by the CPMG pulse sequence. The method was applied to the quantitative analysis of total glucose in blood plasma from human subjects undergoing the oral glucose tolerance test in the teaching hospital, and the results were compared to those obtained using a standard glucose oxidase method in a hospital chemical pathology laboratory. The accuracy of the results obtained using the WATR-CPMG method were generally within 5% of the glucose oxidase method. The coefficient of variation was determined to be better than 4% using plasma samples of diabetic subjects. Application to the quantitative analysis of orange and guava juice was also successfully demonstrated.     

Quantitative fractography of WC-Co cermets by Auger spectroscopy

A general procedure has been developed to determine the area fraction occupied by the binder on the fracture surfaces of cemented carbides. The area fraction of binder on the fracture surface was obtained from the relative peak-to-peak height ratios of elements in the binder and the carbide content was measured by Auger spectroscopy on the fracture surface and an adjacent polished section and the volume fraction of binder present in the cermet. This procedure was employed to determine the area fraction of binder on the fracture surfaces of WC-Co cermets with different binder contents and carbide grain sizes. The average binder mean free path and the area fraction of binder together yield the amount of plastically deformed binder per unit area of fracture surface. The volume of deformed binder and its in situ yield strength were combined to obtain a term proportional to the amount of plastic work done per unit area of fracture surface. It is shown that the correlation between this plastic work term and the fracture toughness of the cermets is good, while correlation with binder mean free path alone is poor.     

Analysis of extracellular matrix production in artificial cartilage constructs by histology, immunocytochemistry, mass spectrometry, and NMR spectroscopy

Artificial cartilage constructs based on primary porcine chondrocytes embedded in agarose gel were cultivated for six weeks under static, free swelling conditions. Standard biochemical assays, immunocytochemical staining methods, MALDI-TOF mass spectrometry, and non-invasive 13C solid-state NMR spectroscopy were used to assess cell proliferation, chondrocyte metabolism, extracellular matrix composition, matrix production, and the nanoarchitecture of the macromolecules in the constructs. In particular the production of sulphated glycosaminoglycans such as chondroitin sulphate was investigated quantitatively. Standard methods such as histological and immunocytochemical tools as well as spectrophotometric assays indicated the production of extracellular matrix in the artificial cartilage constructs. In addition, MALDI-TOF mass spectrometric data allowed to clearly identify the production of chondroitin sulphate in the tissue engineered cartilage. While all these methods require invasive sample treatment, 13C NMR spectroscopy allows to study the composition of the artificial cartilage constructs without previous manipulations. Though lower in sensitivity, 13C NMR spectra clearly showed the presence of chondroitin sulphate in the constructs. To increase the sensitivity of the NMR method, a culture medium that contained uniformly 13C labelled glucose but no sodium pyruvate or L-glutamine was used. Thus, further insights into the chondrocyte metabolism ex vivo are possible. Therefore, MALDI-TOF mass spectrometry and 13C solid-state NMR are useful experimental techniques that can assist the quantitative evaluation and quality control of artificially engineered tissues.     

Quantitative analysis of vitamin A degradation by Raman spectroscopy

Vitamin A is known to support cell growth promotion, maintenance, and differentiation of epithelial tissues. Retinol is currently used in cosmetic formulations and products to deliver these and other benefits to the skin. However, retinol is known to be unstable and, therefore, remains of great concern to the cosmetic industry. The decomposition pathways of the retinoids in general have been previously postulated and investigated mostly by high-performance liquid chromatography (HPLC) with UV/Vis spectroscopy. In our studies, we examined specific conditions at which retinol degrades and subsequently identified and quantified the products of retinol decomposition by Raman spectroscopy. We reveal which experimental settings and computational tools allow monitoring of in situ evolution of an all-trans retinol solution when submitted to UV light in the presence of oxygen.     

Quantitative analysis of adsorbed proteins by X-ray photoelectron spectroscopy

Protein adsorption at solid surfaces is central to many phenomena of medical and technological interest. The determination of the amount of protein attached to the surface is a critical measurement performed by using a wide range of methods. X-ray photoelectron spectroscopy (XPS) is able to provide a straightforward quantitative analysis of the amount of protein adsorbed as an overlayer on a material surface. While XPS is commonly employed to assess qualitatively the amount of adsorbed protein, this is usually expressed in terms of the elemental fraction (or at. %) of nitrogen calculated using an assumption of depth homogeneity despite the fact that this does not linearly scale with the amount of protein. In this paper, we have shown that thicknesses derived from XPS data linearly correlated with spectroscopic ellipsometry data on the same samples with a scatter of 10%. A straightforward equation to convert the concentration of nitrogen from XPS into an equivalent thickness of a protein film is presented. We highlight some discrepancies in the absolute thicknesses determined by XPS and ellipsometry on dried films and quartz crystal microbalance on wet films, which appear likely to result from the inclusion of a contribution from water in the latter two techniques.     

Molecular motions of banana-shaped liquid crystals studied by NMR spectroscopy

Recent studies based on NMR spectroscopy put in evidence the occurrence of a slow motion regime in bent-shaped liquid crystals having the aromatic core formed by five phenyl rings linked by ester groups both in the isotropic and in the nematic phases. In this paper a brief overview of these NMR studies is presented and additional new relaxation data recorded on a banana-shaped mesogen are reported and discussed. In particular, proton spin-lattice relaxation times, T₁, were acquired at different Larmor frequencies from 8 MHz to 5 kHz by means of NMR relaxometry in a wide range of temperatures from the isotropic to the crystalline phases. These data confirm that NMR relaxation in bent-core liquid crystals is affected by much slower dynamics than that observed in common rod-like liquid crystals and that overall molecular reorientations are responsible of this slow motion regime. This finding is discussed in the frame of the results obtained by means of several NMR methods, such as ²H NMR T₂ analysis and ¹H self-diffusion NMR measurements, on the same bent-core molecule.     

Solution of water networks by sparse matrix methods

A computer program for Water Network analysis has been developed usingy sparse matrix techniques for solution. The method used is the successive linearization method where the set of equations [Q]=[Y][H] is solved. In the process, two subroutines for node reordering to preserve sparsity of the Jacobian matrix and a subroutine for solving the matrix by the Doolittle method are included. The method is user oriented and requires a minimum amount of input data and effort. Networks of up to 200 nodes and 300 pipes may be analysed on an IBM 1130 computer with 16K words of memory.     

Quantitative measurements of amino acids by terahertz time-domain transmission spectroscopy

The quantitative analysis of amino acids by terahertz (THz) time-domain absorption spectroscopy is demonstrated. The optical densities of the amino acids were found to be linearly proportional to the concentration. The molar absorption coefficients of L-glutamic acid (L-Glu), L-glutamic acid sodium salt (Na-L-Glu), L-glutamic acid hydrochloric salt (HCl-L-Glu), L-cysteine (L-Cys), and L-histidine (L-His) were calculated by averaging the THz spectra of the amino acids at several different concentrations in approximately the 0.2-1.0 mol L(-1) range. The concentrations of L-Glu, L-Cys, and L-His mixed samples were successfully calculated with errors of less than 11% and 20% when their concentrations were higher than 0.45 and 0.22 mol L(-1), respectively, by using the obtained molar absorption coefficient.     

Quantitative analysis of polyethylene blends by Fourier transform infrared spectroscopy

The quantitative analysis of binary polyethylene (PE) blends by Fourier transform infrared (FT-IR) spectroscopy has been achieved based on the ratio of two absorbance peaks in an FT-IR spectrum. The frequencies for the absorbance ratio are selected based on structural entities of the PE components in the blend. A linear relationship between the absorbance ratio and the blend composition was found to exist if one of the absorbance peaks is distinct to one of the components and the other peak is common to both components. It was also found that any peak resulting from short-chain branching in copolymers (such as linear low-density polyethylene (LLDPE) or metallocene-catalyzed LLDPE (mLLDPE)), is suitable for use as the peak that is designated as being distinct to that component. In order to optimize the linearity of the equation, however, the selection of the second common peak is the most important and depends on the blend system studied. Indeed, under certain circumstances peaks that are not spectrally distinct can be used successfully to apply the method. The method exhibits potential for the routine analysis of PE blends that have been calibrated prior to its application.     

Contactless NMR spectroscopy on a chip

Inductively coupled planar resonators offer convenient integration of high-resolution NMR spectroscopy with microfluidic lab-on-a-chip devices. Planar spiral resonators are fabricated lithographically either by gold electroplating or by etching Cu laminated with polyimide. Their performance is characterized by NMR imaging as well as spectroscopy. A single-scan limit of detection LOD(t) = 0.95 nmol s(1/2) was obtained from sample volumes around 1 μL. The sensitivity of this approach is similar to that obtained by microstripline and microslot probes.     

Quantitative NMR spectroscopy using coaxial inserts containing a reference standard: purity determinations for military nerve agents.

A novel 31P NMR method for the determination of purity for the military nerve agents sarin, soman, and VX has been developed. In contrast to more conventional quantitative NMR methods, stem coaxial inserts are placed into the sample tube to introduce reference material into the analysis without mixing or reaction with the analyte. All sample preparation is eliminated, and the analysis is completed expeditiously in less than 25 min. The method is highly specific and rugged with respect to operator-induced variability, experimental parameters, and all influences from nuclear magnetic relaxation. Nerve agent purity can be determined with a precision and accuracy typically better than 1%, and impurities can be detected at concentrations as low as 25 microg/mL. The limit of quantitation has been estimated at 85 microg/mL. In terms of precision, accuracy and execution time, the method rivals typical chromatographic methods.     

On the use of the matrix pencil method for deep level transientspectroscopy: MP-DLTS

A new approach to capacitance transient analysis, based on the matrix pencil (MP) method, is proposed for deep level transient spectroscopy (DLTS) (MP-DLTS). The MP method offers the least statistical variance of the estimates in the presence of noise. Simulation tests have shown this method to lead to a significant improvement in DLTS resolution even for low trap concentrations. Its noise sensitivity and resolution are quantified and compared with five different DLTS analysis techniques. The MP-DLTS method is found to outperform both DLTS spectrum and direct transient analysis techniques. An experimental investigation of the electrically active defects induced by a germanium preamorphization step prior to dopant implantation was undertaken using the MP-DLTS method. Two electron traps were detected in all samples and characterized