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1.
Magn Reson Med ; 2024 Jun 24.
Artículo en Inglés | MEDLINE | ID: mdl-38924176

RESUMEN

PURPOSE: To fully characterize the orientation dependence of magnetization transfer (MT) and inhomogeneous MT (ihMT) measures in the whole white matter (WM), for both single-fiber and crossing-fiber voxels. METHODS: A characterization method was developed using the fiber orientation obtained from diffusion MRI (dMRI) with diffusion tensor imaging (DTI) and constrained spherical deconvolution. This allowed for characterization of the orientation dependence of measures in all of WM, regardless of the number of fiber orientation in a voxel. Furthermore, the orientation dependence inside 31 different WM bundles was characterized to evaluate the homogeneity of the effect. Variation of the results within and between-subject was assessed from a 12-subject dataset. RESULTS: Previous results for single-fiber voxels were reproduced and a novel characterization was produced in voxels of crossing fibers, which seems to follow trends consistent with single-fiber results. Heterogeneity of the orientation dependence across bundles was observed, but homogeneity within similar bundles was also highlighted. Differences in behavior between MT and ihMT measures, as well as the ratio and saturation versions of these, were noted. CONCLUSION: Orientation dependence characterization was proven possible over the entirety of WM. The vast range of effects and subtleties of the orientation dependence on MT measures showed the need for, but also the challenges of, a correction method.

2.
Magn Reson Med ; 89(5): 1809-1824, 2023 05.
Artículo en Inglés | MEDLINE | ID: mdl-36511247

RESUMEN

PURPOSE: We investigated the correlation, reproducibility, and effect of white matter fiber orientation for three myelin-sensitive MRI techniques: magnetization transfer ratio (MTR), inhomogeneous magnetization transfer ratio (ihMTR), and gradient and spin echo-derived myelin water fraction (MWF). METHODS: We measured the three metrics in 17 white and three deep grey matter regions in 17 healthy adults at 3 T. RESULTS: We found a strong correlation between ihMTR and MTR (r = 0.70, p < 0.001) and ihMTR and MWF (r = 0.79, p < 0.001), and a weaker correlation between MTR and MWF (r = 0.54, p < 0.001). The dynamic range in white matter was greatest for MWF (2.0%-27.5%), followed by MTR (14.4%-23.2%) and then ihMTR (1.2%-5.4%). The average scan-rescan coefficient of variation for white matter regions was 0.6% MTR, 0.3% ihMTR, and 0.7% MWF in metric units; however, when adjusted by the dynamic range, these became 6.3%, 6.1% and 2.8%, respectively. All three metrics varied with fiber direction: MWF and ihMTR were lower in white matter fibers perpendicular to B0 by 6% and 1%, respectively, compared with those parallel, whereas MTR was lower by 0.5% at about 40°, with the highest values at 90°. However, separating the apparent orientation dependence by white matter region revealed large dissimilarities in the trends, suggesting that real differences in myelination between regions are confounding the apparent orientation dependence measured using this method. CONCLUSION: The strong correlation between ihMTR and MWF suggests that these techniques are measuring the same myelination; however, the larger dynamic range of MWF may provide more power to detect small differences in myelin.


Asunto(s)
Vaina de Mielina , Sustancia Blanca , Humanos , Adulto , Reproducibilidad de los Resultados , Encéfalo/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Sustancia Blanca/diagnóstico por imagen , Agua , Biomarcadores
3.
NMR Biomed ; 36(8): e4925, 2023 08.
Artículo en Inglés | MEDLINE | ID: mdl-36908074

RESUMEN

This work aimed to demonstrate an essential phase shift ε 0 for better quantifying R 2 and R 2 * in human brain white matter (WM), and to further elucidate its origin related to the directional diffusivities from standard diffusion tensor imaging (DTI). ε 0 was integrated into a proposed generalized transverse relaxation model for characterizing previously published R 2 and R 2 * orientation dependence profiles in brain WM, and then comparisons were made with those without ε 0 . It was theorized that anisotropic diffusivity direction ε was collinear with an axon fiber subject to all eigenvalues and eigenvectors from an apparent diffusion tensor. To corroborate the origin of ε 0 , R 2 orientation dependences referenced by ε were compared with those referenced by the standard principal diffusivity direction Φ at b-values of 1000 and 2500 (s/mm2 ). These R 2 orientation dependences were obtained from T 2 -weighted images (b = 0) of ultrahigh-resolution Connectome DTI datasets in the public domain. A normalized root-mean-square error ( NRMSE % ) and an F -test were used for evaluating curve-fittings, and statistical significance was considered to be a p of 0.05 or less. A phase-shifted model resulted in significantly reduced NRMSE % compared with that without ε 0 in quantifying various R 2 and R 2 * profiles, both in vivo and ex vivo at multiple B 0 fields. The R 2 profiles based on Φ manifested a right-shifted phase ( ε 0 > 0 ) at two b-values, while those based on ε became free from ε 0 . For all phase-shifted R 2 and R 2 * profiles, ε 0 generally depended on the directional diffusivities by tan - 1 D ⊥ / D ∥ , as predicted. In summary, a ubiquitous phase shift ε 0 has been demonstrated as a prerequisite for better quantifying transverse relaxation orientation dependences in human brain WM. Furthermore, the origin of ε 0 associated with the directional diffusivities from DTI has been elucidated. These findings could have a significant impact on interpretations of prior R 2 and R 2 * datasets and on future research.


Asunto(s)
Sustancia Blanca , Humanos , Sustancia Blanca/diagnóstico por imagen , Imagen de Difusión Tensora/métodos , Encéfalo/diagnóstico por imagen , Imagen de Difusión por Resonancia Magnética , Axones , Anisotropía
4.
Neuroimage ; 241: 118442, 2021 11 01.
Artículo en Inglés | MEDLINE | ID: mdl-34339831

RESUMEN

Multiple studies have reported a significant dependence of the effective transverse relaxation rate constant (R2*) and the phase of gradient-echo based (GRE) signal on the orientation of white matter fibres in the human brain. It has also been hypothesized that magnetic susceptibility, as obtained by single-orientation quantitative susceptibility mapping (QSM), exhibits such a dependence. In this study, we investigated this hypothesized relationship in a cohort of healthy volunteers. We show that R2* follows the predicted orientation dependence consistently across white matter regions, whereas the apparent magnetic susceptibility is related differently to fibre orientation across the brain and often in a complex non-monotonic manner. In addition, we explored the effect of fractional anisotropy measured by diffusion-weighted MRI on the strength of the orientation dependence and observed only a limited influence in many regions. However, with careful consideration of such an impact and the limitations imposed by the ill-posed nature of the dipole inversion process, it is possible to study magnetic susceptibility anisotropy in specific brain regions with a single orientation acquisition.


Asunto(s)
Encéfalo/diagnóstico por imagen , Encéfalo/fisiología , Imagen de Difusión por Resonancia Magnética/métodos , Orientación/fisiología , Sustancia Blanca/diagnóstico por imagen , Sustancia Blanca/fisiología , Adulto , Anciano , Anisotropía , Estudios de Cohortes , Imagen de Difusión por Resonancia Magnética/normas , Femenino , Humanos , Masculino , Persona de Mediana Edad , Adulto Joven
5.
Magn Reson Med ; 82(5): 1804-1811, 2019 11.
Artículo en Inglés | MEDLINE | ID: mdl-31293007

RESUMEN

PURPOSE: To propose and validate an efficient method, based on a biophysically motivated signal model, for removing the orientation-dependent part of R2* using a single gradient-recalled echo (GRE) measurement. METHODS: The proposed method utilized a temporal second-order approximation of the hollow-cylinder-fiber model, in which the parameter describing the linear signal decay corresponded to the orientation-independent part of R2* . The estimated parameters were compared to the classical, mono-exponential decay model for R2* in a sample of an ex vivo human optic chiasm (OC). The OC was measured at 16 distinct orientations relative to the external magnetic field using GRE at 7T. To show that the proposed signal model can remove the orientation dependence of R2* , it was compared to the established phenomenological method for separating R2* into orientation-dependent and -independent parts. RESULTS: Using the phenomenological method on the classical signal model, the well-known separation of R2* into orientation-dependent and -independent parts was verified. For the proposed model, no significant orientation dependence in the linear signal decay parameter was observed. CONCLUSIONS: Since the proposed second-order model features orientation-dependent and -independent components at distinct temporal orders, it can be used to remove the orientation dependence of R2* using only a single GRE measurement.


Asunto(s)
Imagen por Resonancia Magnética/métodos , Sustancia Blanca/diagnóstico por imagen , Autopsia , Biofisica , Humanos , Procesamiento de Imagen Asistido por Computador/métodos , Masculino , Persona de Mediana Edad
6.
Nano Lett ; 15(6): 3770-9, 2015 Jun 10.
Artículo en Inglés | MEDLINE | ID: mdl-25879390

RESUMEN

The rapid development of ultrascaled III-V compound semiconductor devices urges the detailed investigation of metal-semiconductor contacts at nanoscale where crystal orientation, size, and structural phase play dominant roles in device performance. Here, we report the first study on the solid-state reaction between metal (Ni) and ternary III-V semiconductor (In0.53Ga0.47As) nanochannels to reveal the reaction kinetics, formed crystal structure, and interfacial properties. We observe a size-dependent Ni surface diffusion dominant kinetic process that gradually departs to a volume diffusion process as the Fin width increases, as properly depicted with our Fin-specific growth model. The interfacial relationship was found to be Ni4InGaAs2 (0001) ∥ In0.53Ga0.47As (111) with a single Ni4InGaAs2 phase whose [0001] axis exhibit a peculiar rotation away from the nickelide/InGaAs interface due to surface energy minimization. This crystalline interfacial relationship is responsible for introducing a uniaxial height expansion of 33% ± 5% in the formed nickelide segments. Further, the nickelide formation resulted in both in-plane and out-of-plane compressive strains in the Fin channels, significantly altering the In0.53Ga0.47As energy band-edge structure near the interface with a peak bandgap energy of ∼1.26 eV. These timely observations advance our understanding and development for self-aligned contacts to III-V nanochannels and for engineering new processes that can maximize their device performance.

7.
Neuroimage ; 114: 136-46, 2015 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-25862261

RESUMEN

Quantification of magnetization-transfer (MT) experiments is typically based on a model comprising a liquid pool "a" of free water and a semisolid pool "b" of motionally restricted macromolecules or membrane compounds. By a comprehensive fitting approach, high quality MT parameter maps of the human brain are obtained. In particular, a distinct correlation between the diffusion-tensor orientation with respect to the B0-magnetic field and the apparent transverse relaxation time, T2(b), of the semisolid pool (i.e., the width of its absorption line) is observed. This orientation dependence is quantitatively explained by a refined dipolar lineshape for pool b that explicitly considers the specific geometrical arrangement of lipid bilayers wrapped around a cylindrical axon. The model inherently reduces the myelin membrane to its lipid constituents, which is motivated by previous studies on efficient interaction sites (e.g., cholesterol or galactocerebrosides) in the myelin membrane and on the origin of ultrashort T2 signals in cerebral white matter. The agreement between MT orientation effects and corresponding forward simulations using empirical diffusion imaging results as input as well as results from fits employing the novel lineshape support previous suggestions that the fiber orientation distribution in a voxel can be modeled as a scaled Bingham distribution.


Asunto(s)
Química Encefálica , Campos Magnéticos , Vaina de Mielina/química , Sustancia Blanca/química , Adulto , Simulación por Computador , Difusión , Imagen de Difusión por Resonancia Magnética , Imagen de Difusión Tensora , Femenino , Humanos , Masculino , Modelos Neurológicos , Adulto Joven
8.
Sci Rep ; 14(1): 12961, 2024 06 05.
Artículo en Inglés | MEDLINE | ID: mdl-38839823

RESUMEN

A variation of the longitudinal relaxation time T 1 in brain regions that differ in their main fiber direction has been occasionally reported, however, with inconsistent results. Goal of the present study was to clarify such inconsistencies, and the origin of potential T 1 orientation dependence, by applying direct sample rotation and comparing the results from different approaches to measure T 1 . A section of fixed porcine spinal cord white matter was investigated at 3 T with variation of the fiber-to-field angle θ FB . The experiments included one-dimensional inversion-recovery, MP2RAGE, and variable flip-angle T 1 measurements at 22 °C and 36 °C as well as magnetization-transfer (MT) and diffusion-weighted acquisitions. Depending on the technique, different degrees of T 1 anisotropy (between 2 and 10%) were observed as well as different dependencies on θ FB (monotonic variation or T 1 maximum at 30-40°). More pronounced anisotropy was obtained with techniques that are more sensitive to MT effects. Furthermore, strong correlations of θ FB -dependent MT saturation and T 1 were found. A comprehensive analysis based on the binary spin-bath model for MT revealed an interplay of several orientation-dependent parameters, including the transverse relaxation times of the macromolecular and the water pool as well as the longitudinal relaxation time of the macromolecular pool.


Asunto(s)
Médula Espinal , Agua , Sustancia Blanca , Animales , Sustancia Blanca/diagnóstico por imagen , Sustancia Blanca/fisiología , Porcinos , Anisotropía , Médula Espinal/fisiología , Protones , Rotación
9.
J Neural Eng ; 20(3)2023 05 31.
Artículo en Inglés | MEDLINE | ID: mdl-37187172

RESUMEN

Objective.The objective of this study was to investigate the effects of micromagnetic stimuli strength and frequency from theMagneticPen(MagPen) on the rat right sciatic nerve. The nerve's response was measured by recording muscle activity and movement of the right hind limb.Approach.The MagPen was custom-built to be stably held over the sciatic nerve. Rat leg muscle twitches were captured on video, and movements were extracted using image processing algorithms. EMG recordings were also used to measure muscle activity.Main results.The MagPen prototype, when driven by an alternating current, generates a time-varying magnetic field, which, according to Faraday's law of electromagnetic induction, induces an electric field for neuromodulation. The orientation-dependent spatial contour maps of the induced electric field from the MagPen prototype have been numerically simulated. Furthermore, in thisin vivowork onµMS, a dose-response relationship has been reported by experimentally studying how varying the amplitude (Range: 25 mVp-pthrough 6Vp-p) and frequency (range: 100 Hz through 5 kHz) of the MagPen stimuli alters hind limb movement. The primary highlight of this dose-response relationship (repeated overnrats, wheren= 7) is that for aµMS stimuli of higher frequency, significantly smaller amplitudes can trigger hind limb muscle twitch. This frequency-dependent activation can be justified by Faraday's Law, which states that the magnitude of the induced electric field is directly proportional to the frequency.Significance.This work reports thatµMS can successfully activate the sciatic nerve in a dose-dependent manner. The impact of this dose-response curve addresses the controversy in this research community about whether the stimulation from theseµcoils arise from a thermal effect or micromagnetic stimulation. MagPen probes do not have a direct electrochemical interface with tissue and therefore do not experience electrode degradation, biofouling, and irreversible redox reactions like traditional direct contact electrodes. Magnetic fields from theµcoils create more precise activation than electrodes because they apply more focused and localized stimulation. Finally, unique features ofµMS, such as the orientation dependence, directionality, and spatial specificity, have been discussed.


Asunto(s)
Músculo Esquelético , Nervio Ciático , Ratas , Animales , Nervio Ciático/fisiología , Músculo Esquelético/fisiología , Electrodos , Estimulación Eléctrica/métodos
10.
ACS Nano ; 16(3): 3604-3612, 2022 Mar 22.
Artículo en Inglés | MEDLINE | ID: mdl-35263102

RESUMEN

Previous studies on ultrasound-propelled nano- and microparticles have considered only systems in which the particle orientation is perpendicular to the direction of propagation of the ultrasound. However, in future applications of these particles, they will typically be able to attain other orientations. Therefore, using direct acoustofluidic simulations, here we study how the propulsion of triangular nano- and microparticles, which are known to have a particularly efficient acoustic propulsion and are therefore promising candidates for future applications, depends on their orientation relative to the propagation direction of a traveling ultrasound wave. Our results reveal that the propulsion of the particles depends strongly on their orientation relative to the direction of wave propagation and that the particles tend to orient perpendicularly to the wave direction. We also address the orientation-averaged translational and angular velocities of the particles, which correspond to the particles' effective propulsion for an isotropic exposure to ultrasound. Our results allow assessment of how free ultrasound-propelled colloidal particles move in three spatial dimensions and thus constitute an important step toward the realization of envisaged future applications of such particles.

11.
Neuroimage Clin ; 35: 103059, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-35661471

RESUMEN

Quantitative susceptibility mapping (QSM) has been successfully applied to study changes in deep grey matter nuclei as well as in lesional tissue, but its application to white matter has been complicated by the observed orientation dependence of gradient echo signal. The anisotropic susceptibility tensor is thought to be at the origin of this orientation dependence, and magnetic susceptibility anisotropy (MSA) derived from this tensor has been proposed as a marker of the state and integrity of the myelin sheath and may therefore be of particular interest for the study of demyelinating pathologies such as multiple sclerosis (MS). Reconstruction of the susceptibility tensor, however, requires repeated measurements with multiple head orientations, rendering the approach impractical for clinical applications. In this study, we combined single-orientation QSM with fibre orientation information to assess apparent MSA in three white matter tracts, i.e., optic radiation (OR), splenium of the corpus callosum (SCC), and superior longitudinal fascicle (SLF), in two cohorts of 64 healthy controls and 89 MS patients. The apparent MSA showed a significant decrease in optic radiation in the MS cohort compared with healthy controls. It decreased in the MS cohort with increasing lesion load in OR and with disease duration in the splenium. All of this suggests demyelination in normal appearing white matter. However, the apparent MSA observed in the SLF pointed to potential systematic issues that require further exploration to realize the full potential of the presented approach. Despite the limitations of such single-orientation ROI-specific estimation, we believe that our clinically feasible approach to study degenerative changes in WM is worthy of further investigation.


Asunto(s)
Esclerosis Múltiple , Sustancia Blanca , Anisotropía , Humanos , Fenómenos Magnéticos , Imagen por Resonancia Magnética , Esclerosis Múltiple/diagnóstico por imagen , Esclerosis Múltiple/patología , Vaina de Mielina , Sustancia Blanca/diagnóstico por imagen , Sustancia Blanca/patología
12.
Cognition ; 209: 104559, 2021 04.
Artículo en Inglés | MEDLINE | ID: mdl-33388527

RESUMEN

In the past several decades, considerable theoretical progress has been made in understanding the role of reference frames in the encoding and retrieval of spatial information about the environment. Many of these insights have come from participants making judgments of relative direction using their memories of spatial layouts. In this task, participants are asked to imagine standing at a given location and facing a certain direction, and to point to a target location. Although this task has been widely and productively used, a computational cognitive model of judgments of relative direction has yet to be introduced. Computational modeling of judgments of relative direction is a critical next step to formulating and testing hypotheses about the cognitive processes involved in establishing and using spatial reference frames. We present an initial attempt to model judgments of relative direction and fit the model to two datasets exhibiting behavioral patterns commonly observed in the spatial memory literature. The model was able to predict many important features of these data, most notably alignment effects. We discuss directions for future modeling efforts.


Asunto(s)
Juicio , Percepción Espacial , Cognición , Humanos , Solución de Problemas , Memoria Espacial
13.
Front Psychol ; 11: 393, 2020.
Artículo en Inglés | MEDLINE | ID: mdl-32210896

RESUMEN

The proficiency of human observers to identify body postures is examined in three experiments. We use a posture decision task in which participants are primed with either anatomically possible or impossible postures (in the latter case the upper and lower body face in opposite directions). In a long-term priming paradigm (i.e., in an initial priming block of trials and a subsequent test phase several minutes later), we manipulate the relation between priming and test postures with respect to the identity of the person in the body postures (Experiment 1), the prototypicality of the depth orientations (Experiment 2), and the variability of the priming orientations (Experiment 3). Reaction time to the test postures is the main dependent variable. In Experiment 1 it is found that priming of postures does not depend on the exact visual appearance of the actor (either same priming and test female or male figure or different figures), supporting the hypothesis that posture priming primarily is determined by the spatial relations between the body parts and much less by characteristics of the person involved. Long-term priming in our paradigm apparently is based on the reactivation of high-level posture representations that make abstraction of the identity of the human figure. In Experiment 2 we observe that privileged or prototypical orientations (e.g., 3/4 views) do not affect long-term priming of body postures. In Experiment 3, we find that increasing or decreasing the variability between the priming and test figures influences reaction time performance. Collectively, these results provide a better understanding of the flexibility (e.g., invariant to identity) and limits (e.g., depending on depth orientation) of the processes supporting human posture recognition.

14.
Materials (Basel) ; 11(12)2018 Dec 02.
Artículo en Inglés | MEDLINE | ID: mdl-30513846

RESUMEN

Through a coordinate transformation approach, crystal orientation dependences of elastic and piezoelectric properties at room temperature have been investigated in a three-dimensional space for rhombohedral bismuth ferrite (BiFeO3). Elastic constants (stiffnesses) c11', c12', c13' and piezoelectric constants d15', d31', d33' along arbitrary orientations were obtained based on crystalline asymmetry characteristics of 3m point group BiFeO3. Parameters along specific orientations obtaining the largest values were presented. The max c11' = 213 × 108 N/m² could be achieved in planes with ϕ = 0° and 90°. The max c12' = c13' = 132.2 × 108 N/m² could be achieved along directions at θ = 13° and θ = 77° inside three mirror planes, respectively. The max d15' = 27.6 × 10-12 C/N and the max d31' = 12.67 × 10-12 C/N could be both obtained along directions at θ = 69° inside mirror planes. The max d33' = 18 × 10-12 C/N could be obtained at θ = 0°, along the spontaneous polarization axis. By adopting optimal directions, the elastic and piezoelectric parameters of BiFeO3 could be significantly enhanced which shows applications for the growth of BeFeO3 films with preferred orientations and enhanced properties.

15.
J Magn Reson ; 290: 38-45, 2018 05.
Artículo en Inglés | MEDLINE | ID: mdl-29550514

RESUMEN

Interpretation of saturation-recovery EPR experiments on nitroxide spin labels whose angular rotation is restricted by the orienting potential of the environment (e.g., membranes) currently concentrates on the influence of rotational rates and not of molecular order. Here, I consider the dependence on molecular ordering of contributions to the rates of electron spin-lattice relaxation and cross relaxation from modulation of N-hyperfine and Zeeman anisotropies. These are determined by the averages 〈cos2θ〉 and 〈cos4θ〉, where θ is the angle between the nitroxide z-axis and the static magnetic field, which in turn depends on the angles that these two directions make with the director of uniaxial ordering. For saturation-recovery EPR at 9 GHz, the recovery rate constant is predicted to decrease with increasing order for the magnetic field oriented parallel to the director, and to increase slightly for the perpendicular field orientation. The latter situation corresponds to the usual experimental protocol and is consistent with the dependence on chain-labelling position in lipid bilayer membranes. An altered dependence on order parameter is predicted for saturation-recovery EPR at high field (94 GHz) that is not entirely consistent with observation. Comparisons with experiment are complicated by contributions from slow-motional components, and an unexplained background recovery rate that most probably is independent of order parameter. In general, this analysis supports the interpretation that recovery rates are determined principally by rotational diffusion rates, but experiments at other spectral positions/field orientations could increase the sensitivity to order parameter.

16.
Nanomaterials (Basel) ; 8(4)2018 Mar 23.
Artículo en Inglés | MEDLINE | ID: mdl-29570639

RESUMEN

Due to the enhanced piezoelectric properties, excellent mechanical properties and tunable electric properties, one-dimensional (1D) piezoelectric materials have shown their promising applications in nanogenerators (NG), sensors, actuators, electronic devices etc. To present a clear view about 1D piezoelectric materials, this review mainly focuses on the characterization and optimization of the piezoelectric properties of 1D nanomaterials, including semiconducting nanowires (NWs) with wurtzite and/or zinc blend phases, perovskite NWs and 1D polymers. Specifically, the piezoelectric coefficients, performance of single NW-based NG and structure-dependent electromechanical properties of 1D nanostructured materials can be respectively investigated through piezoresponse force microscopy, atomic force microscopy and the in-situ scanning/transmission electron microcopy. Along with the introduction of the mechanism and piezoelectric properties of 1D semiconductor, perovskite materials and polymers, their performance improvement strategies are summarized from the view of microstructures, including size-effect, crystal structure, orientation and defects. Finally, the extension of 1D piezoelectric materials in field effect transistors and optoelectronic devices are simply introduced.

17.
ACS Appl Mater Interfaces ; 8(40): 27332-27338, 2016 Oct 12.
Artículo en Inglés | MEDLINE | ID: mdl-27652690

RESUMEN

Chirality is one of the essential features in our living life and exerts a wide variety of applications in enantio-adsorption/separation. However, the mechanism between chirality and enantio-adsorption/separation is very significant in homochiral porous materials; in particular, the understanding of the relationship between crystalline orientations and chiral behavior is a challenging but important mechanism. In this work, homochiral porous crystalline metal organic framework (MOF) materials were grown on hydroxyl- and carboxyl-functionalized substrates, resulting in homochiral porous thin films with different orientations. The enantioselectivity and adsorption rates in two different oriented homochiral porous thin films were studied by using gas-phase quartz crystal microbalance (QCM) experiment of chiral probe molecules. The different mass uptake and time constant showed that the chiral behavior can be obviously influenced by the crystalline orientations on the same homochiral porous thin films. This study will not only offer a good model to understand the mechanism of chiral behavior in homochiral porous materials but also provide guidance for developing new homochiral-oriented porous thin films with high enantioselectivity or enantioseparation.

18.
ACS Appl Mater Interfaces ; 8(20): 13157-65, 2016 05 25.
Artículo en Inglés | MEDLINE | ID: mdl-27153212

RESUMEN

Reactions in the gas phase are of primary technological importance for applications in nano- and microfabrication technology and in the semiconductor industry. We present exclusively gas-phase protocols to chemically passivate oxide-free Si(111) and Si(100) surfaces with short-chain alkynes. The resulting surfaces showed equal or better oxidation resistance than most existing liquid-phase-derived surfaces and rivaled the outstanding stability of a full-coverage Si(111)-propenyl surface.1,2 The most stable surface (Si(111)-ethenyl) grew one-fifth of a monolayer of oxide (0.04 nm) after 1 month of air exposure. We monitored the regrowth of oxides on passivated Si(111) and Si(100) surfaces by X-ray photoelectron spectroscopy (XPS) and observed a significant crystal-orientation dependence of initial rates when total oxide thickness was below approximately one monolayer (0.2 nm). This difference was correlated with the desorption kinetics of residual surface Si-F bonds formed during HF treatment. We discuss applications of the technology and suggest future directions for process optimization.

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