Search

The aim of this study was the development of collagen and collagen/auricular cartilage scaffolds for application in dermal regeneration. Collagen was obtained from bovine tendon by a 72 h-long treatment, while bovine auricular cartilage was treated for 24 h and divided into two parts, external (perichondrium, E) and internal (elastic cartilage, I). The scaffolds were prepared by mixing collagen (C) with the internal part (CI) or the external part (CE) in a 3:1 ratio. Differential scanning calorimetry, scanning electron microscopy (SEM) analysis, microcomputed tomography imaging (micro-CT) and swelling degree were used to characterize the scaffolds. Cytotoxicity, cell adhesion, and cell proliferation assays were performed using the cell line NIH/3T3. All samples presented a similar denaturation temperature (Td) around 48 °C, while CE presented a second Td at 51.2 °C. SEM micrographs showed superficial pores in all scaffolds and micro-CT exhibited interconnected pore spaces with porosity above 60% (sizes between 47 and 149 µm). The order of swelling was CE < CI < C and the scaffolds did not present cytotoxicity, showing attachment rates above 75%-all samples showed a similar pattern of proliferation until 168 h, whereas CI tended to decrease after this time. The scaffolds were easily obtained, biocompatible and had adequate morphology for cell growth. All samples showed high adhesion, whereas collagen-only and collagen/external part scaffolds presented a better cell proliferation rate and would be indicated for possible use in dermal regeneration., (© 2020. Springer Nature B.V.)

The Redfield master equation was solved analytically for a nuclear system with spin I=7/2. Using the irreducible tensor operator basis, the solutions of each density matrix element were computed. The experimental setup consisted of the 133 Cs nuclei of the cesium-pentadecafluorooctanoate molecule in a lyotropic liquid crystal sample in the nematic phase at room temperature. Experimental longitudinal and transverse magnetization dynamics of the 133 Cs nuclei were monitored, and the theoretical approach was used to generate valuable mathematical expressions with the highest accuracy through numerical procedures. This methodology can be extended to other nuclei with minimal difficulties., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Caking is associated with the consolidation of dry powder and granules, leading to losses of function and/or quality. It has been object of studies in the pharmaceutical, food and fertiliser areas since 1920's because of its significant impact on product quality and value. Caking has been described as a three-step event consisting of sorption-dissolution-recrystallisation phases and constitutes a critical factor in fertilisers losses during storage while also hampering fertiliser application. Current methods for the evaluation of water sorption dynamics are expensive, time-consuming and/or inaccurate. This manuscript describes an unprecedented application of low-field 1 H NMR relaxometry for the kinetic study of humidity uptake, in real-time, by urea mixed with different concentrations of an anti-caking agent (zeolite). The proposed method allows to follow the water uptake in different domains of the mixed fertiliser/zeolite samples. To our knowledge, this dynamic has not been observed and quantified so far in real-time. Furthermore, we presented the use of 2D-ILT for kinetic studies, being the first dimension the usual transverse relaxation and the second dimension the kinetic one. With this approach, the NMR relaxation times T 2 correlated to time constants associated with the uptake kinetics of the water. This method could be extended to several kinetic studies and experiments with temperature variation. Depending on the kinetics of the studied process, the kernel of the Laplace transform must be suitably adapted., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Inc. All rights reserved.)

High-resolution computed micro-tomography is an important area of science, which correlates well with several experimental methodologies and serves as a basis for advanced computational physics studies, in which high-resolution images are used as input to different scientific simulation models. The dataset presented herein includes (raw) grayscale images obtained using the Bruker Skyscan 1272 X-Ray tomograph; filtered images acquired through contrast enhancement and noise reduction filters; and segmented images obtained by using the IsoData segmentation method. All images have a resolution of 2.25 µm (isometric voxels) and size of 1000 3  voxels., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Author(s). Published by Elsevier Inc.)

The aim of this study was to investigate the filling ability of a new premixed bioceramic sealer in comparison with an epoxy resin-based sealer in curved root canals using different segmentation methods and voxel sizes in micro-CT images. Twelve curved mesial roots of mandibular molars with two separated canals were selected. All root canals were prepared by using HyFlex EDM files size 25/.08 and filled by the single cone technique and Bio-C Sealer or AH Plus (n = 12). The samples were scanned by micro-CT at 5 μm. The images were analyzed at 5, 10, and 20 μm for the volumetric analysis of voids in filling. Visual image segmentation was performed by two examiners, and the automatic segmentation was accomplished for comparison. Radiopacity of the sealers was evaluated by radiographic analysis. Data were submitted to the two-way ANOVA and non-paired t tests at a significance level of 5%. AH Plus had the highest radiopacity (p < .05). Root canals filled with AH Plus or Bio-C had similar low percentage of voids (p > .05). There was no difference interobserver, which had similar results to those obtained with automatic segmentation for all voxel sizes evaluated (p > .05). Bio-C Sealer had appropriate filling ability. Visual and automatic segmentation can be applied to micro-CT images with voxel sizes from 5 to 20 μm to evaluate the filling of sealers with adequate radiopacity. Automatic segmentation should be used as a faster method., (© 2021 Wiley Periodicals LLC.)

The aim of this study was to assess the influence of micro-computed tomography (micro-CT) voxel size on dentinal microcrack detection after root canal preparation using rotary heat-treated nickel-titanium files. Curved mesial root canals (n = 24) of mandibular molars were prepared using ProDesign Logic 30/.05 (PDL) or HyFlex EDM 25/.08 (HEDM). The specimens were scanned by micro-CT at 5 μm voxel size before and after root canal preparation. The percentage of microcracks was evaluated in images at 5, 10 and 20 μm voxel size, by two examiners at two moments. The Kappa and McNemar tests (α = 0.05) were used. The percentage of dentinal microcracks was similar before and after PDL and HEDM preparations, at 10 and 20 μm (p > 0.05). HEDM showed a higher percentage of dentinal microcracks in the middle third at 5 μm after preparation (p < 0.05). The detection of dentinal microcracks before and after instrumentation using PDL was more accurate at 5 μm than at 20 μm, in all thirds (p < 0.05). Within the limitations of this ex vivo study, as expected, the results showed that different resolutions influence the micro-CT analysis of microcracks. The highest accuracy in detecting microcracks was observed for analyses performed at 5 μm voxel size. HyFlex EDM caused even more microcracks to develop in the middle third, detectable only by visualization of images made at 5 μm voxel size.

Permeability is the key parameter for quantifying fluid flow in porous rocks. Knowledge of the spatial distribution of the connected pore space allows, in principle, to predict the permeability of a rock sample. However, limitations in feature resolution and approximations at microscopic scales have so far precluded systematic upscaling of permeability predictions. Here, we report fluid flow simulations in pore-scale network representations designed to overcome such limitations. We present a novel capillary network representation with an enhanced level of spatial detail at microscale. We find that the network-based flow simulations predict experimental permeabilities measured at lab scale in the same rock sample without the need for calibration or correction. By applying the method to a broader class of representative geological samples, with permeability values covering two orders of magnitude, we obtain scaling relationships that reveal how mesoscale permeability emerges from microscopic capillary diameter and fluid velocity distributions.

This article was written in honor of Prof. Bernhard Blümich, who has heavily impacted many areas of Magnetic Resonance and, in particular, low-field and portable NMR with numerous advances, concepts, innovations, and applications of this impressive technology. Many years ago, we decided to research and develop single-sided magnets for the area of petroleum science and engineering to study oil reservoir rocks in the laboratory under well-logging conditions. The global urge to exploit oil reserves requires the analysis of reservoirs, intending to characterize the yields before starting the production. Thus, well-logging tools have been developed to estimate the quality of oil and reservoir productivity. NMR logging is included in these analytical tools, and numerous operations using this kind of device were performed since the early 1950s. To contribute to this vital research area, we show the development of a new benchtop single-sided NMR system, with well-logging tool characteristics, a cylindrical sweet spot with 4 cm of diameter and length, with magnetic field of 47 mT centered at 11 cm from the magnet's surface and a constant gradient of 35.7 G/cm along z. This system was used in self-diffusion, T 1 -T 2 , and D-T 2 measurements of standard liquids and rock cores, demonstrating its functionality., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Longitudinal relaxation time (T 1 ), transverse relaxation time (T 2 ) and diffusion coefficient (D) values have been widely used for the characterizations of materials using low field Time Domain Nuclear Magnetic Resonance (TD-NMR). Each parameter can be determined using one-dimensional techniques or their values and correlations by multi-dimensional experiments such as T 1 -T 2 , D-T 2 , and T 1 -D-T 2 . In this work, we studied four D-T 1 sequences for TD-NMR combining Stejskal-Tanner Pulse Gradient Spin Echo (PGSE) diffusion measurement with Inversion-Recovery (IR), Saturation-Recovery (SR), Small-Angle Continuous Wave Free Precession (CWFP-T 1 ) and Small-Angle Flip-Flop (SAFF) for T 1 measurement. The results show that rapid D-T 1 measurements can be obtained with single shot CWFP-T 1 and SAFF sequences. The two sequences were two and eight time fast than sequences based on SR and IR, respectively. Although the two fast sequences yield low signal-to-noise ratio signal, they can be as fast as the traditional D-T 2 experiment, or even faster, because it is not necessary to wait a recycle delay of 5 T 1 . Another advantage of the CWFP-T 1 and SAFF methods, when compared to the one based on SR or CPMG (for D-T 2 ) are the low specific absorption rate (SAR) of these sequences due the low flip angles in the sequences, that reduces the sample heating problem. These sequences were initially studied using phantom samples. They also were used to study plant tissues to observe the anisotropic diffusion in asparagus. Therefore, they can be useful methods for practical application in TD-NMR., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

The aim of this study was to evaluate volumetric and morphological stability of 3 root-end filling materials in addition to porosity and interface voids, using micro-computed tomography (µCT) in high resolution and a highly accurate approach for image analysis. Following root-end resection and apical preparation, two-rooted maxillary premolars were divided into three groups, according to the filling materials: White MTA Angelus, Biodentine, and IRM. Samples were scanned by µCT at 5 µm after the setting time and at time intervals of 7 and 30 days after immersion in phosphate-buffered saline (PBS). Volumetric and morphological changes besides material porosity and interface voids were evaluated by comparing initial values and those obtained after immersion. Data were analyzed statistically, using ANOVA and t-tests (α = 0.05). All materials showed volumetric stability. Regarding the morphological changes, Biodentine had a significant thickness reduction after storage in PBS when compared with MTA. Biodentine also showed an increase in porosity, as well as in percentage and thickness of voids after 30 days of immersion. In conclusion, µCT in high resolution and an accurate image analysis approach may be used to evaluate morphological changes of endodontic materials. Although Biodentine showed suitable adaptability and lower values of porosity than MTA, after PBS immersion there was a dimensional reduction of this material, besides an increase in porosity and interface voids.

The usual Nuclear Magnetic Resonance (NMR) experiments for measuring spin-lattice relaxation time (T 1 ) distributions are Inversion-Recovery (IR) and Saturation-Recovery (SR), followed by data processing based on ill-posed multi-exponential curve fitting methods. Recently, a new method combining SR and IR, called Saturation-Inversion-Recovery (SIR), has been proposed to obtain sharper T 1 -dependences than IR and SR. In this article, we propose an appropriate combination of SIR signals to directly obtain T 1 distributions without using any multi-exponential fitting methods., (Copyright © 2019 Elsevier Inc. All rights reserved.)

The Inversion-Recovery (IR) technique has already been proposed to be used as a T 1 -filter for T 2 -T 2 Exchange experiments. However, when the Exchange experiments are employed for studying samples that show T 1 distributions, where the pools are defined by broad relaxation time distributions, e.g. porous media, IR might be difficult to be used as a filter. This paper presents the difficulties found when using IR and proposes the use of Saturation-Recovery (SR) technique as an alternative to T 1 -filter., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Nowadays, most of the efforts in NMR applied to porous media are dedicated to studying the molecular fluid dynamics within and among the pores. These analyses have a higher complexity due to morphology and chemical composition of rocks, besides dynamic effects as restricted diffusion, diffusional coupling, and exchange processes. Since the translational nuclear spin diffusion in a confined geometry (e.g. pores and fractures) requires specific boundary conditions, the theoretical solutions are restricted to some special problems and, in many cases, computational methods are required. The Random Walk Method is a classic way to simulate self-diffusion along a Digital Porous Medium. Bergman model considers the magnetic relaxation process of the fluid molecules by including a probability rate of magnetization survival under surface interactions. Here we propose a statistical approach to correlate surface magnetic relaxivity with the computational method applied to the NMR relaxation in order to elucidate the relationship between simulated relaxation time and pore size of the Digital Porous Medium. The proposed computational method simulates one- and two-dimensional NMR techniques reproducing, for example, longitudinal and transverse relaxation times (T 1 and T 2 , respectively), diffusion coefficients (D), as well as their correlations. For a good approximation between the numerical and experimental results, it is necessary to preserve the complexity of translational diffusion through the microstructures in the digital rocks. Therefore, we use Digital Porous Media obtained by 3D X-ray microtomography. To validate the method, relaxation times of ideal spherical pores were obtained and compared with the previous determinations by the Brownstein-Tarr model, as well as the computational approach proposed by Bergman. Furthermore, simulated and experimental results of synthetic porous media are compared. These results make evident the potential of computational physics in the analysis of the NMR data for complex porous materials., (Copyright © 2018 Elsevier Inc. All rights reserved.)

The NMR measurements of longitudinal and transverse relaxation times and its multidimensional correlations provide useful information about molecular dynamics. However, these experiments are very time-consuming, and many researchers proposed faster experiments to reduce this issue. This paper presents a new way to simultaneously perform T 2 -T 2 Exchange and T 1 -T 2 correlation experiments by taking the advantage of the storage time and the two steps phase cycling used for running the relaxation exchange experiment. The data corresponding to each step is either summed or subtracted to produce the T 2 -T 2 and T 1 -T 2 data, enhancing the information obtained while maintaining the experiment duration. Comparing the results from this technique with traditional NMR experiments it was possible to validate the method., (Copyright © 2018 Elsevier Inc. All rights reserved.)

This work introduces an alternative way to perform the T2 - T2 Exchange NMR experiment. Rather than varying the number of π pulses in the first CPMG cycle of the T2 - T2 Exchange NMR pulse sequence, as used to obtain the 2D correlation maps, it is fixed and small enough to act as a short T2-filter. By varying the storage time, a set of 1D measurements of T2 distributions can be obtained to reveal the effects of the migration dynamics combined with relaxation effects. This significantly reduces the required time to perform the experiment, allowing a more in-depth study of exchange dynamics and relaxation processes with improved signal-to-noise ratio. These aspects stand as basis of this novel experiment, T2-Filtered T2 - T2 Exchange NMR or simply T2 F-TREx.

We have produced and characterized spin-squeezed states at a temperature of 26 °C in a nuclear magnetic resonance quadrupolar system. The experiment was carried out on 133Cs nuclei of spin I=7/2 in a sample of lyotropic liquid crystal. The source of spin squeezing was identified as the interaction between the quadrupole moment of the nuclei and the electric field gradients present within the molecules. We use the spin angular momentum representation to describe formally the nonlinear operators that produce the spin squeezing on a Hilbert space of dimension 2I+1=8. The quantitative and qualitative characterization of this spin-squeezing phenomenon is expressed by a squeezing parameter and squeezing angle developed for the two-mode Bose-Einstein condensate system, as well as by the Wigner quasiprobability distribution function. The generality of the present experimental scheme points to potential applications in solid-state physics.

Background: Enzymatic hydrolysis is a crucial step of biomass conversion into biofuels and different pretreatments have been proposed to improve the process efficiency. Amongst the various factors affecting hydrolysis yields of biomass samples, porosity and water accessibility stand out due to their intimate relation with enzymes accessibility to the cellulose and hemicellulose fractions of the biomass. In this work, sugarcane bagasse was subjected to acid and alkali pretreatments. The changes in the total surface area, hydrophilicity, porosity and water accessibility of cellulose were investigated by scanning electron microscopy (SEM) and nuclear magnetic resonance (NMR)., Results: Changes in chemical and physical properties of the samples, caused by the partial removal of hemicellulose and lignin, led to the increase in porosity of the cell walls and unwinding of the cellulose bundles, as observed by SEM. (1)H NMR relaxation data revealed the existence of water molecules occupying the cores of wide and narrow vessels as well as the cell wall internal structure. Upon drying, the water molecules associated with the structure of the cell wall did not undergo significant dynamical and partial moisture changes, while those located in the cores of wide and narrow vessels kept continuously evaporating until reaching approximately 20% of relative humidity. This indicates that water is first removed from the cores of lumens and, in the dry sample, the only remaining water molecules are those bound to the cell walls. The stronger interaction of water with pretreated bagasse is consistent with better enzymes accessibility to cellulose and higher efficiency of the enzymatic hydrolysis., Conclusions: We were able to identify that sugarcane bagasse modification under acid and basic pretreatments change the water accessibility to different sites of the sample, associated with both bagasse structure (lumens and cell walls) and hydrophilicity (lignin removal). Furthermore, we show that the substrates with increased water accessibility correspond to those with higher hydrolysis yields and that there is a correlation between experimentally NMR-measured transverse relaxation times and the efficiency of enzymatic hydrolysis. This might allow for semiquantitative estimates of the enzymatic hydrolysis efficiency of biomass samples using inexpensive and non-destructive low-field (1)H NMR relaxometry methods.

We report the experimental measurement of bipartite quantum correlations of an unknown two-qubit state. Using a liquid state Nuclear Magnetic Resonance setup and employing geometric discord, we evaluate the quantum correlations of a state without resorting to prior knowledge of its density matrix. The method is applicable to any 2 ⊗ d system and provides, in terms of number of measurements required, an advantage over full state tomography scaling with the dimension d of the unmeasured subsystem. The negativity of quantumness is measured as well for reference. We also observe the phenomenon of sudden transition of quantum correlations when local phase and amplitude damping channels are applied to the state.

In this study, Cross-Polarization Magic-angle Spinning CP/MAS, 2D Exchange, Centerband-Only Detection of Exchange (CODEX), and Separated-Local-Field (SLF) NMR experiments were used to study the molecular dynamics of poly(ethylene glycol) (PEG) inside Hectorite/PEG intercalation compounds in both single- and double-layer configurations. The results revealed that the overall amplitude of the motions of the PEG chain in the single-layer configuration is considerably smaller than that observed for the double-layer intercalation compound. This result indicates that the effect of having the polymer chain interacting with both clay platelets is to produce a substantial decrease in the motional amplitudes of those chains. The presence of these dynamically restricted segments might be explained by the presence of anchoring points between the clay platelets and the PEG oxygen atoms, which was induced by the Na⁺ cations. By comparing the PEG motional amplitudes of the double-layered nanocomposites composed of polymers with different molecular weights, a decrease in the motional amplitude for the smaller PEG chain was observed, which might also be understood using the presence of anchoring points.

Nuclear magnetic resonance is viewed as an important technique for the implementation of many quantum information algorithms and protocols. Although the most straightforward approach is to use the two-level system composed of spin 1/2 nuclei as qubits, quadrupolar nuclei, which possess a spin greater than 1/2, are being used as an alternative. In this study, we show some unique features of quadrupolar systems for quantum information processing, with an emphasis on the ability to execute efficient quantum state tomography (QST) using only global rotations of the spin system, whose performance is shown in detail. By preparing suitable states and implementing logical operations by numerically optimized pulses together with the QST method, we follow the stepwise execution of Grover's algorithm. We also review some work in the literature concerning the relaxation of pseudo-pure states in spin 3/2 systems as well as its modelling in both the Redfield and Kraus formalisms. These data are used to discuss differences in the behaviour of the quantum correlations observed for two-qubit systems implemented by spin 1/2 and quadrupolar spin 3/2 systems, also presented in the literature. The possibilities and advantages of using nuclear quadrupole resonance experiments for quantum information processing are also discussed.

In this paper we present a series of high-resolution zero-field NMR spectra of the polycrystalline intermetallic compound GdAl(2). The spectra were obtained with the sample at 4.2K in the ordered magnetic state and in the absence of an external static magnetic field. Using a sequence composed of two RF pulses, we obtained up to five multi-quantum echoes for the (27)Al nuclei, which were used to construct the zero-field NMR spectra. The spectra obtained from the FID observed after the second pulse and the even echoes exhibited higher resolution than the odd ones. In order to explain such behavior, we propose a model in which there are two regions inside the sample with different inhomogeneous spectral-line broadenings. Moreover, with the enhanced resolution from the FID signal, we were able to determine quadrupolar couplings with great precision directly from the respective spectra. These results were compared with those obtained from the quadrupolar oscillations of the echo signals, and showed good agreement. Similar data were also obtained from (155)Gd and (157)Gd nuclei., (Copyright © 2011 Elsevier Inc. All rights reserved.)

Nonclassical correlations play a crucial role in the development of quantum information science. The recent discovery that nonclassical correlations can be present even in separable (nonentangled) states has broadened this scenario. This generalized quantum correlation has been increasing in relevance in several fields, among them quantum communication, quantum computation, quantum phase transitions, and biological systems. We demonstrate here the occurrence of the sudden-change phenomenon and immunity against some sources of noise for the quantum discord and its classical counterpart, in a room temperature nuclear magnetic resonance setup. The experiment is performed in a decohering environment causing loss of phase relations among the energy eigenstates and exchange of energy between system and environment, resulting in relaxation to the Gibbs ensemble.

The quantification of quantum correlations (other than entanglement) usually entails labored numerical optimization procedures also demanding quantum state tomographic methods. Thus it is interesting to have a laboratory friendly witness for the nature of correlations. In this Letter we report a direct experimental implementation of such a witness in a room temperature nuclear magnetic resonance system. In our experiment the nature of correlations is revealed by performing only few local magnetization measurements. We also compared the witness results with those for the symmetric quantum discord and we obtained a fairly good agreement.

The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and 13C Nuclear Magnetic Resonance (13C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Autoregressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the 13C NMR spectra clearly differentiates sediment samples closer to the Subaé estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

This article describes a solid-state NMR (SSNMR) investigation of the influence of hydration and chemical cross-linking on the molecular dynamics of the constituents of the bovine pericardium (BP) tissues and its relation to the mechanical properties of the tissue. Samples of natural phenethylamine-diepoxide (DE)- and glutaraldehyde (GL)-fixed BP were investigated by (13)C cross-polarization SSNMR to probe the dynamics of the collagen, and the results were correlated to the mechanical properties of the tissues, probed by dynamical mechanical analysis. For samples of natural BP, the NMR results show that the higher the hydration level the more pronounced the molecular dynamics of the collagen backbone and sidechains, decreasing the tissue's elastic modulus. In contrast, in DE- and GL-treated samples, the collagen molecules are more rigid, and the hydration seems to be less effective in increasing the collagen molecular dynamics and reducing the mechanical strength of the samples. This is mostly attributed to the presence of cross-links between the collagen plates, which renders the collagen mobility less dependent on the water absorption in chemically treated samples., (2010 John Wiley & Sons, Ltd.)

We have studied the molecular dynamics of one of the major macromolecules in articular cartilage, chondroitin sulfate. Applying (13)C high-resolution magic-angle spinning NMR techniques, the NMR signals of all rigid macromolecules in cartilage can be suppressed, allowing the exclusive detection of the highly mobile chondroitin sulfate. The technique is also used to detect the chondroitin sulfate in artificial tissue-engineered cartilage. The tissue-engineered material that is based on matrix producing chondrocytes cultured in a collagen gel should provide properties as close as possible to those of the natural cartilage. Nuclear relaxation times of the chondroitin sulfate were determined for both tissues. Although T(1) relaxation times are rather similar, the T(2) relaxation in tissue-engineered cartilage is significantly shorter. This suggests that the motions of chondroitin sulfate in natural and artificial cartilage are different. The nuclear relaxation times of chondroitin sulfate in natural and tissue-engineered cartilage were modeled using a broad distribution function for the motional correlation times. Although the description of the microscopic molecular dynamics of the chondroitin sulfate in natural and artificial cartilage required the identical broad distribution functions for the correlation times of motion, significant differences in the correlation times of motion that are extracted from the model indicate that the artificial tissue does not fully meet the standards of the natural ideal. This could also be confirmed by macroscopic biomechanical elasticity measurements. Nevertheless, these results suggest that NMR is a useful tool for the investigation of the quality of artificially engineered tissue., ((c) 2010 Wiley Periodicals, Inc.)

Guanylate cyclase-activating protein-2 (GCAP-2) is a retinal Ca(2+) sensor protein. It plays a central role in shaping the photoreceptor light response and in light adaptation through the Ca(2+)-dependent regulation of the transmembrane retinal guanylate cyclase (GC). GCAP-2 is N-terminally myristoylated and the full activation of the GC requires this lipid modification. The structural and functional role of the N-terminus and particularly of the myristoyl moiety is currently not well understood. In particular, detailed structural information on the myristoylated N-terminus in the presence of membranes was not available. Therefore, we studied the structure and dynamics of a 19 amino acid peptide representing the myristoylated N-terminus of GCAP-2 bound to lipid membranes by solid-state NMR. (13)C isotropic chemical shifts revealed a random coiled secondary structure of the peptide. Peptide segments up to Ala(9) interact with the membrane surface. Order parameters for Calpha and side chain carbons obtained from DIPSHIFT experiments are relatively low, suggesting high mobility of the membrane-associated peptide. Static (2)H solid-state NMR measurements show that the myristoyl moiety is fully incorporated into the lipid membrane. The parameters of the myristoyl moiety and the DMPC host membrane are quite similar. Furthermore, dynamic parameters (obtained from (2)H NMR relaxation rates) of the peptide's myristic acid chain are also comparable to those of the lipid chains of the host matrix. Therefore, the myristoyl moiety of the N-terminal peptide of GCAP-2 fills a similar conformational space as the surrounding phospholipid chains., (Copyright 2009 Elsevier B.V. All rights reserved.)

This paper presents a description of nuclear magnetic resonance (NMR) of quadrupolar systems using the Holstein-Primakoff (HP) formalism and its analogy with a Bose-Einstein condensate (BEC) system. Two nuclear spin systems constituted of quadrupolar nuclei I=3/2 ((23)Na) and I=7/2 ((133)Cs) in lyotropic liquid crystals were used for experimental demonstrations. Specifically, we derived the conditions necessary for accomplishing the analogy, executed the proper experiments, and compared with quantum mechanical prediction for a Bose system. The NMR description in the HP representation could be applied in the future as a workbench for BEC-like systems, where the statistical properties may be obtained using the intermediate statistic, first established by Gentile. The description can be applied for any quadrupolar systems, including new developed solid-state NMR GaAS nanodevices.

This article reports a relaxation study in an oriented system containing spin 3/2 nuclei using quantum state tomography (QST). The use of QST allowed evaluating the time evolution of all density matrix elements starting from several initial states. Using an appropriated treatment based on the Redfield theory, the relaxation rate of each density matrix element was measured and the reduced spectral densities that describe the system relaxation were determined. All the experimental data could be well described assuming pure quadrupolar relaxation and reduced spectral densities corresponding to a superposition of slow and fast motions. The data were also analyzed in the context of Quantum Information Processing, where the coherence loss of each qubit of the system was determined using the partial trace operation.

In this report, the application of a class of separated local field NMR experiments named dipolar chemical shift correlation (DIPSHIFT) for probing motions in the intermediate regime is discussed. Simple analytical procedures based on the Anderson-Weiss (AW) approximation are presented. In order to establish limits of validity of the AW based formulas, a comparison with spin dynamics simulations based on the solution of the stochastic Liouville-von-Neumann equation is presented. It is shown that at short evolution times (less than 30% of the rotor period), the AW based formulas are suitable for fitting the DIPSHIFT curves and extracting kinetic parameters even in the case of jumplike motions. However, full spin dynamics simulations provide a more reliable treatment and extend the frequency range of the molecular motions accessible by DIPSHIFT experiments. As an experimental test, molecular jumps of imidazol methyl sulfonate and trimethylsulfoxonium iodide, as well as the side-chain motions in the photoluminescent polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylenevinylene], were characterized. Possible extensions are also discussed.

We present a minor but essential modification to the CODEX 1D-MAS exchange experiment. The new CONTRA method, which requires minor changes of the original sequence only, has advantages over the previously introduced S-CODEX, since it is less sensitive to artefacts caused by finite pulse lengths. The performance of this variant, including the finite pulse effect, was confirmed by SIMPSON calculations and demonstrated on a number of dynamic systems.

In this paper, we describe a quantum state tomography method based on global rotations of the spin system which, together with a coherence selection scheme, enables the complete density matrix reconstruction. The main advantage of this technique, in respect to previous proposals, is the use of much shorter rf pulses, which decreases significantly the time necessary for algorithm quantum state tomography. In this case, under adequate experimental conditions, the rf pulses correspond to simple spatial rotations of the spin states, and its analytical description is conveniently given in the irreducible tensor formalism. Simulated results show the feasibility of the method for a single spin 72 nucleus. As an experimental result, we exemplify the application of this method by tomographing the steps during the implementation of the Deutsch algorithm. The algorithm was implemented in a (23)Na quadrupole nucleus using the strongly modulated pulses technique. We also extended the tomography method for a 3-coupled homonuclear spin 12 system, where an additional evolution under the internal Hamiltonian is necessary for zero order coherences evaluation.

The compositions of humic acids (HAs) isolated from cultivated and forested "Terra Preta de Indio" or Amazonian Dark Earth soils (anthropogenic soils) were compared with those from adjacent non-anthropogenic soils (control soils) using elemental and thermogravimetric analyses, and a variety of solid-state nuclear magnetic resonance techniques. The thermogravimetric index, which indicates the molecular thermal resistance, was greater for the anthropogenic soils than for the control soils suggesting polycyclic aromatic components in the former. The cultivated anthropogenic soils were more enriched in C and depleted in H than the anthropogenic soils under forest, as the result of the selective degradation of aliphatic structures and the possible enrichment of H-deficient condensed aromatic structures. The combination of variable amplitude cross-polarization (VACP) and chemical shift anisotropy with total suppression of spinning sidebands experiments with composite pi pulses could be used to quantify the aromaticity of the HAs from the anthropogenic soils. From principal component analysis, using the VACP spectra, it was possible to separate the different constituents of the HAs, such as the carboxylated aromatic structures, from the anthropogenic soils and plant derived compounds. The data show that the HAs from anthropogenic soils have high contents of aryl and ionisable oxygenated functional groups, and the major functionalities from adjacent control soils are oxygenated functional groups from labile structures (carbohydrates, peptides, and with evidence for lignin structures). The anthropogenic soils HAs can be considered to be more recalcitrant, and with more stable reactive functional groups which may, in part, explain their more sustainable fertility due to the organic matter contribution to the soil cation exchange capacity.

There are difficulties in quantifying and characterising the organic matter (OM) in soils that contain significant amounts of partially oxidised char or charcoal materials. The anthropogenic black carbon (BC), such as that found in the Terra Preta de Indio soils of the Amazon region, is a good example of the OM that is difficult to analyse in such soils. (13)C direct polarisation/magic angle spinning (DP/MAS) at high MAS frequency, (1)H-(13)C cross polarisation (CP)/MAS with total suppression of spinning sidebands (TOSS), and chemical shift anisotropy (CSA) filter nuclear magnetic resonance techniques have been applied successfully for quantifying the different components of OM. However, because pyrogenic materials present strong local magnetic susceptibility heterogeneities, the use of CSA-filter and TOSS make the pulse sequences very sensitive to imperfections in the pi pulses. In this study, the DP/MAS pulse sequence was replaced by a CP with a radio frequency ramp--variable amplitude CP (VACP)--VACP/MAS pulse sequence, and composite pi pulses were used in the CSA-filter and TOSS pulse sequences. In that way, the component functionalities in a humic acid from a BC soil were successfully determined. The spectrometer time needed was greatly decreased by employing this VACP/MAS technique. This development provides an accurate method for characterising BC-rich samples from different origins.

This article presents the realization of many self-reversible quantum logic gates using two-qubit quadrupolar spin 3/2 systems. Such operations are theoretically described using propagation matrices for the RF pulses that include the effect of the quadrupolar evolution during the pulses. Experimental demonstrations are performed using a generalized form of the recently developed method for quantum state tomography in spin 3/2 systems. By doing so, the possibility of controlling relative phases of superimposed pseudo-pure states is demonstrated. In addition, many aspects of the effect of the quadrupolar evolution, occurring during the RF pulses, on the quantum operations performance are discussed. Most of the procedures presented can be easily adapted to describe selective pulses of higher spin systems (>3/2) and for spin 1/2 under J couplings.

One-dimensional (1D) exchange NMR experiments can elucidate the geometry, time scale, memory, and heterogeneity of slow molecular motions (1 ms-1 s) in solids. The one-dimensional version of pure-exchange (PUREX) solid-state exchange NMR, which is applied to static samples and uses the chemical shift anisotropy as a probe for molecular motion, is particularly promising and convenient in applications where site resolution is not a problem, i.e., in systems with few chemical sites. In this work, some important aspects of the 1D PUREX experiment applied to systems with complex molecular motions are analyzed. The influence of intermediate-regime (10 micros-1 ms) motions and of the distribution of reorientation angles on the pure-exchange intensity are discussed, together with a simple method for estimating the activation energy of motions occurring with a single correlation time. In addition, it is demonstrated that detailed information on the motional geometry can be obtained from 1D PUREX spectral line shapes. Experiments on a molecular crystal, dimethyl sulfone, confirm the analysis quantitatively. In two amorphous polymers, atactic polypropylene (aPP) and polyisobutylene (PIB), which differ only by one methyl group in the repeat unit, the height of the normalized exchange intensity clearly reveals a striking difference in the width of the distribution of correlation times slightly above the glass transition. The aPP shows the broad distribution and Williams-Landel-Ferry temperature dependence of correlation times typical of polymers and other "fragile" glass formers. In contrast, the dynamics in PIB occur essentially with a single correlation time and exhibits Arrhenius behavior, which is more typical of "strong" glass formers; this is somewhat surprising given the weak intermolecular forces in PIB.

We report solid-state NMR investigations of the effect of temperature and hydration on the molecular mobility of collagen isolated from bovine achilles tendon. (13)C cross-polarization magic angle spinning (MAS) experiments were performed on samples at natural abundance, using NMR methods that detect motionally averaged dipolar interactions and chemical shift anisotropies and also slow reorientational processes. Fast motions with correlation times much shorter than 40 micro s scale dipolar couplings and chemical shift anisotropies of the carbon sites in collagen. These motionally averaged anisotropic interactions provide a measure of the amplitudes of the segmental motions expressed by a molecular order parameter. The data reveal that increasing hydration has a much stronger effect on the amplitude of the molecular processes than increasing temperature. In particular, the Cgamma carbons of the hydroxyproline residues exhibit a strong dependence of the amplitude of motion on the hydration level. This could be correlated with the effect of hydration on the hydrogen bonding structure in collagen, for which this residue is known to play a crucial role. The applicability of 1D MAS exchange experiments to investigate motions on the millisecond time-scale is discussed and first results are presented. Slow motions with correlation times of the order of milliseconds have also been detected for hydrated collagen., (Copyright 2004 John Wiley & Sons, Ltd.)

This work describes a numerical methodology to obtain more efficient relaxation filters to selectively retain or remove components based on relaxation times. The procedure uses linear combinations of spectra with various recycle or filter delays to obtain components that are both quantitative and pure. Modulation profiles are calculated assuming exponential relaxation behavior. The method is general and can be applied to a wide range of solution or solid-state NMR experiments including direct-polarization (DP), or filtered cross-polarization (CP) spectra. 13C NMR experiments on isotactic poly(1-butene) and dimethyl sulfone showed the utility of the technique for selectively suppressing peaks.

13C high-resolution solid-state nuclear magnetic resonance (NMR) was employed to study carbon materials prepared through the thermal decomposition of four different organic precursors (rice hulls, endocarp of babassu coconut, peat, and PVC). For heat treatment temperatures (HTTs) above about 600 C, all materials presented 13C NMR spectra composed of a unique resonance line associated with carbon atoms in aromatic planes. With increasing HTT a continuous broadening of this resonance and a diamagnetic shift in its central frequency were verified for all samples. The evolution of the magnitude and anisotropy of the magnetic susceptibility of the heat-treated carbon samples with HTT explains well these findings. It is shown that these results are better understood when a comparison is made with the features of the 13C NMR spectrum of polycrystalline graphite, for which the magnetic susceptibility effect is also present and is much more pronounced.

One- and two-dimensional 13C exchange nuclear magnetic resonance experiments under magic-angle spinning (MAS) can provide detailed information on slow segmental reorientations and chemical exchange in organic solids, including polymers and proteins. However, observations of dynamics on the time scale of seconds or longer are hampered by the competing process of dipolar 13C spin exchange (spin diffusion). In this Communication, we show that fast MAS can significantly slow down the dipolar spin exchange effect for unprotonated carbon sites. The exchange is measured quantitatively using the centerband-only detection of exchange technique, which enables the detection of exchange at any spinning speed, even in the absence of changes of isotropic chemical shifts. For chemically equivalent unprotonated 13C sites, the dipolar spin exchange rate is found to decrease slightly less than proportionally with the sample-rotation frequency, between 8 and 28 kHz. In the same range, the dipolar spin exchange rate for a glassy polymer with an inhomogeneously broadened MAS line decreases by a factor of 10. For methylene groups, no or only a minor slow-down of the exchange rate is found., (Copyright 2001 Academic Press.)

Three exchange nuclear magnetic resonance (NMR) techniques are presented that yield (13)C NMR spectra exclusively of slowly reorienting segments, suppressing the often dominant signals of immobile components. The first technique eliminates the diagonal ridge that usually dominates two-dimensional (2D) exchange NMR spectra and that makes it hard to detect the broad and low off-diagonal exchange patterns. A modulation of the 2D exchange spectrum by the sine-square of a factor which is proportional to the difference between evolution and detection frequencies is generated by fixed additional evolution and detection periods of duration tau, yielding a 2D pure-exchange (PUREX) spectrum. Smooth off-diagonal intensity is obtained by systematically incrementing tau and summing up the resulting spectra. The related second technique yields a static one-dimensional (1D) spectrum selectively of the exchanging site(s), which can thus be identified. Efficient detection of previously almost unobservable slow motions in a semicrystalline polymer is demonstrated. The third approach, a 1D pure-exchange experiment under magic-angle spinning, is an extension of the exchange-induced sideband (EIS) method. A TOSS (total suppression of sidebands) spectrum obtained after the same number of pulses and delays, with a simple swap of z periods, is subtracted from the EIS spectrum, leaving only the exchange-induced sidebands and a strong, easily detected centerband of the mobile site(s)., (Copyright 2000 Academic Press.)