Susceptibility corrections in solid state NMR experiments with oriented membrane samples. Part II: theory

In solid state NMR analysis of oriented biomembranes the samples typically have the shape of a rectangular block, formed by stacking a number of glass slides coated with the membranes under investigation. Reference material may be provided internally in the volume of the block or as an external layer on its surface, as described in the accompanying paper [J. Magn. Reson. 164 (2003) 104-114]. The demagnetizing field resulting in such non-spheroidal samples is inhomogeneous. It shifts and broadens the NMR lines of both the sample and of the reference, as compared to the ideal of a spherical sample. The magnitude of these effects is typically of the order of a few ppm. To determine the necessary corrections, a general analysis is presented here for the demagnetizing field of a layered sample of rectangular block geometry, with the normal of the layers parallel to the main field or tilted about an axis of the block. The correction to the line position of the block sample is found to be approximately equal to that of the spheroid which can be inscribed into the block, and for which the correction is well known. For an external reference layer, placed on top of the block, the correction can be found by the same approximation, invoking a simple mirror concept. The layered structure of the block can be accounted for by using an average magnetic susceptibility. Sample and support materials contribute to that average according to their volume filling factors. If the sample material is anisotropic at the molecular level, as e.g. lipid bilayers are, the resulting anisotropy of the block is reduced by the filling factor of the sample material.     

Superhydrophobic cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent

A superhydrophobic complex coating for cotton fabrics based on silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent (PFSC) was reported in this article. The complex thin film was prepared through a sol-gel process using cotton fabrics as a substrate. Silica nanoparticles in the coating made the textile surface much rougher, and perfluorooctylated quaternary ammonium silane coupling agent on the top layer of the surface lowered the surface free energy. Textiles coated with this coating showed excellent water repellent property, and water contact angle (CA) increased from 133° on cotton fabrics treated with pure PFSC without silica sol pretreatment up to 145°. The oil repellency was also improved and the contact angle of CH₂I₂ droplet on the fabric surface reached to 131°. In contrast, the contact angle of CH₂I₂ on the fabric surface treated with pure PFSC was only 125°.     

Investigations of silicone breast implants with the NMR-MOUSE

Silicone breast implants are used for breast augmentation and breast reconstruction. The issues of concern associated with such implants are: (a) the quality control of each implant before implantation, and (b) the detection of implant bleeding after implantation. We have studied the use of the Nuclear Magnetic Resonance-MObile Universal Surface Explorer (NMR-MOUSE) for the nondestructive testing of (a) the quality of implant shells, and (b) changes in implant gel due to leakage of body fluid into the implant. Depth profiles measured nondestructively through implant shells at different positions of each implant by the Profile NMR-MOUSE assured good reproducibility of the quality and thickness of different shell layers. The leakage of implants upon rupture was mimicked by observing changes in the transverse NMR relaxation time of the implant gel upon ingress of physiological saline solution and safflower oil through the rupture. Results demonstrate that nondestructive testing with unilateral NMR is a potential method for use in the quality control of implants and for the screening of implants for rupture after implantation.     

Profiles with microscopic resolution by single-sided NMR

A single-sided NMR sensor to produce depth profiles with microscopic spatial resolution is presented. It uses a novel permanent magnet geometry that generates a highly flat sensitive volume parallel to the scanner surface. By repositioning the sensitive slice across the object one-dimensional profiles of the sample structure can be produced with a space resolution better than 5 microm. The open geometry of the sensor results in a powerful testing tool to characterize arbitrarily sized objects in a non-destructive way.     

Shaping the Sensitive Volume of a Single-Sided NMR-Sensor to Profile Cylindrical Samples with High Resolution

This work reports the construction of a single-sided magnet generating a sensitive volume with adjustable curvature. It is useful to profile cylindrical samples with high depth resolution. The sensor geometry is based on the Profile NMR-MOUSE, which generates a parabolic field profile with a quadratic coefficient that decreases with the distance from the magnet surface. Such field profiles approximate cylinder walls within limited angular range with negligible deviation. Then, by varying the working depth, shells of different diameter in the sample can be matched. Simulation and experiments conducted on phantoms confirm that a depth resolution of about 35 μm can be obtained. The sensor was used to profile the structure of a cylindric air spring bellows with high resolution. Besides resolving the fiber layers used to reinforce the rubber matrix, the ingress of hexane was detected via T ₂ changes of the material.     

Structure and oil repellency: Textiles with liquid repellency to hexane

Combining structure and liquid repellent coatings to optimise non-wettability is a well-established field. However, the area in recent years has been dominated by data on water repellency. The work here provides data on how certain plant structures can be used to develop surfaces that provide repellency towards both polar and non-polar, low surface tension fluids. Combining fluoropolymer coatings with ‘hairy’ fibres is particularly beneficial for providing liquid-repellent textiles. None of these surfaces can however be regarded as super-repellent to low surface tension liquids (i.e. with little difference in advancing and receding contact angles).     

Time resolved spectroscopic NMR imaging using hyperpolarized Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized ¹²⁹Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

An analytical methodology for magnetic field control in unilateral NMR

Traditionally, unilateral NMR systems such as the NMR-MOUSE have used the fringe field between two bar magnets joined with a yoke in a 'U' geometry. This allows NMR signals to be acquired from a sensitive volume displaced from the magnets, permitting large samples to be investigated. The drawback of this approach is that the static field (B0) generated in this configuration is inhomogeneous, and has a large, nonlinear, gradient. As a consequence, the sensitive volume of the instrument is both small and ill defined. Empirical redesign of the permanent magnet array producing the B0 field has yielded instruments with magnetic field topologies acceptable for varying applications. The drawback of current approaches is the lack of formalism in the control of B0. Rather than tailoring the magnet geometry to NMR investigations, measurements must be tailored to the available magnet geometry. In this work, we present a design procedure whereby the size, shape, field strength, homogeneity, and gradients in the sensitive spot of a unilateral NMR sensor can be controlled. Our design uses high permeability pole pieces, shaped according to the contours of an analytical expression, to control B0, allowing unilateral NMR instruments to be designed to generate a controlled static field topology. We discuss the approach in the context of previously published design techniques, and explain the advantages inherent in our strategy as compared to other optimization methods. We detail the design, simulation, and construction of a unilateral magnet array using our approach. It is shown that the fabricated array exhibits a B0 topology consistent with the design. The utility of the design is demonstrated in a sample nondestructive testing application. Our design methodology is general, and defines a class of unilateral permanent magnet arrays in which the strength and shape of B0 within the sensitive volume can be controlled.     

Time resolved spectroscopic NMR imaging using hyperpolarized 129Xe

We have visualized the melting and dissolution processes of xenon (Xe) ice into different solvents using the methods of nuclear magnetic resonance (NMR) spectroscopy, imaging, and time resolved spectroscopic imaging by means of hyperpolarized 129Xe. Starting from the initial condition of a hyperpolarized solid Xe layer frozen on top of an ethanol (ethanol/water) ice block we measured the Xe phase transitions as a function of time and temperature. In the pure ethanol sample, pieces of Xe ice first fall through the viscous ethanol to the bottom of the sample tube and then form a thin layer of liquid Xe/ethanol. The xenon atoms are trapped in this liquid layer up to room temperature and keep their magnetization over a time period of 11 min. In the ethanol/water mixture (80 vol%/20%), most of the polarized Xe liquid first stays on top of the ethanol/water ice block and then starts to penetrate into the pores and cracks of the ethanol/water ice block. In the final stage, nearly all the Xe polarization is in the gas phase above the liquid and trapped inside the pores. NMR spectra of homogeneous samples of pure ethanol containing thermally polarized Xe and the spectroscopic images of the melting process show that very high concentrations of hyperpolarized Xe (about half of the density of liquid Xe) can be stored or delivered in pure ethanol.     

Synthesis and properties control of fluorinated organic-inorganic hybrid films

Fluorinated organic-inorganic hybrid films were prepared by free-radical random copolymerization and sol-gel process through dodecafluoroheptyl methacrylate (DFMA), vinyltriethoxysilane (VTES), and tetramethoxysilane (TMOS). It was found that the prepared fluorinated organic-inorganic hybrid film was very hydrophobic and exhibits excellent water repellency. Hydrophobic fluorocarbon side chains were preferentially enriched to the outermost layer at the interface of coating film-air, and three layers probably exist in the coating films. The fluorinated hybrid films possessed fluorocarbon side chains orient toward the air originating from DFMA as the top layer, hydrocarbon backbone chain originating from vinyl polymerization as the middle layer, and silica network originating from the hydrolysis and condensation of siloxane as the bottom layer. It demonstrated that most of TMOS added might be arranged to the bottom layer of the fluorinated hybrid films, and had a slight impact on the enrichment of fluorocarbon side chains of the outermost layer. However, the useful properties of the fluorinated organic-inorganic hybrid films such as thickness and corrosion resistant can be significantly improved by the increase of TMOS content.     

High-efficiency 1.5 microm thick optical axis grating and its use for laser beam combining

We demonstrate an optical axis grating (OAG) recorded in a nematic liquid crystal that yields a higher than 80% diffraction efficiency and over 800:1 switching contrast between diffraction orders for a laser beam of a red wavelength in a material layer only 1.5 microm thick. The grating was used for combining two laser beams with high efficiency. These observations prove the feasibility of new generation high-efficiency diffractive optical components, which are most promising for infrared and high-power applications owing to their enhanced transparency and reduced thermal effects in thin material layers.     

Controlling sound absorption by an upstream resistive layer

Resistive screens, or perforated plates, are widely used upstream of porous materials. They can be used either for protection or decoration, or for acoustic properties enhancement. This study points out the role that a resistive layer can have upstream on a porous material. Based on numerical simulations, this work gives the guidelines for rational use of high resistive layers in order to maximize the normal sound absorption of porous multilayers. Two major results emerge: (i) the upstream resistive layer can control the sound absorption of the porous multilayer, while nullifying the acoustic properties of downstream layer and (ii) this upstream layer may be detrimental to sound absorption of porous multilayer. Experimental validation on a porous multilayer, controlled by a woven textile, supports these findings. The sound absorption of material with poor sound absorption performance can be enhanced with a conveniently designed resistive layer.     

Time-Resolved Study of the Photo-Curing Process of Dental Resins with the NMR-MOUSE

The photo-curing reaction of dental resins has been examined with unilateral nuclear magnetic resonance (NMR-MOUSE) allowing nondestructive high-resolution measurement of depth profiles as a function of time and space. The NMR signal is sensitive to both the monomer concentration and changes in molecular mobility. Upon irradiation with blue light, it first increases due to molecular mobility enhanced by the reaction heat and then decreases exponentially with the monomer concentration as the polymer signal is lost in the dead time of the instrument upon curing. The space and time dependence of the NMR signal can be described by the photo-polymerization reaction kinetics together with a heuristic approximation of the temperature dependence.     

NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying ¹H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples. PACS 76.60 k     

On calculating the oscillations of a viscous liquid layer over a solid spherical core in terms of the boundary layer theory

The theory of a boundary layer near the periodically oscillating free surface of a spherical viscous liquid layer over a solid core (bottom) is modified. Two boundary layers are considered to adequately describe a liquid viscous flow in the system: one at the free surface of the liquid and the other at the solid bottom. The thicknesses of the boundary layers are estimated, which provide any given discrepancy between an exact solution to the model problem and a solution obtained in the small viscosity approximation. Taking into account the boundary layer near the solid bottom is shown to be significant only for lower oscillation modes. For higher modes, the flow near the core can be considered potential. In the case of lower modes and shallow liquid, the surface and bottom boundary layers overlap and an eddy flow occupies the entire volume of the liquid.     

Improvement of water and oil repellency on wood substrates by using fluorinated silica nanocoating

We have investigated a one-step fabrication of fluoro-containing silica coating on wooden substrates, showing multi-functions including super repellency toward water and sunflower oil, low sliding angles, good durability, and low adsorption capacity of moisture. The repellent slurry, consisting of well-mixing silica nanospheres and perfluoroalkyl methacrylic copolymer, is simply prepared and subsequently sprayed over wooden substrates with good adhesion. It has shown that the decoration of silica nanospheres on microscaled wooden texture acts as a crucial role in improving the repellency toward water and sunflower oil droplets. The maximal contact angles can reach as high as 168.3° and 153.6° for water and sunflower oil drops, respectively. These analyses of wetted fraction and work of adhesion also demonstrate the improved repellency due to the addition of silica. This improvement of the repellencies is ascribed to the fact that the drops partially sit on F-coated silica spheres, leaving a layer of air underneath the droplet (i.e., Cassie state). On the basis of the results, the multi-functional coating on wooden substrates delivers a promising commercial feasibility on a variety of woodworks.     

Water and oil repellency of flexible silica-coated polymeric substrates

A facile coating technique was used for the one-step creation of silica-sphere layers onto flexible polypropylene (PP) substrates, which showed the enhanced repellency toward liquid droplets with different surface tensions, ranging from 25.6 to 72.3 mN/m. One-step solution preparation comprised the homogenous mixing of colloidal silica nanospheres and perfluoroalkyl methacrylic copolymer, and the resulting F-silica slurry was subsequently deposited over the PP films, which showed good adhesion. The flexible silica-coated polymeric film displayed a remarkable repellency toward water and oil drops, when compared with the F-coated PP flat film. The silica-stacking layers on the PP substrate generated a roughened surface, owing to the creation of bionic surface hierarchically combined with multiple-scale architecture. To clarify this, the wetted fraction was determined from Cassie-Baxter equation, and the work of adhesion, based on Young-Duprè equation, was used to examine the sliding ability of the resulting polymeric films. The cross-cut test incorporated with film bending proved the excellent adherence between silica layer and PP substrate. A satisfactory durability in water and oil immersions for 10 days showed that the resulting PP film possesses strong adhesion and better repellency for a long period, confirming a promising commercial feasibility.     

Investigation of industrial tea-leaf-fibre waste material for its sound absorption properties

The sound absorption of an industrial waste, developed during the processing of tea leaves has been investigated. Three different layers of tea-leaf-fibre waste materials with and without backing provided by a single layer of woven textile cloth were tested for their sound absorption properties. The experimental data indicate that a 1 cm thick tea-leaf-fibre waste material with backing, provides sound absorption which is almost equivalent to that provided by six layers of woven textile cloth. Twenty millimeters thick layers of rigidly backed tea-leaf-fibres and non-woven fibre materials exhibit almost equivalent sound absorption in the frequency range between 500 and 3200 Hz.     

Magnet design with high B(0) homogeneity for fast-field-cycling NMR applications

The design, construction, and performance of a low-inductance solenoidal coil with high B(0) homogeneity for fast-field-cycling NMR is presented. It consists of six concentric layers. The conductor width is varied to minimize the B(0) inhomogeneity in the volume of the sample. This is done using an algorithm which takes the real shape of the conductor directly into account. The calculated coil geometry can be manufactured easily using standard computerized numeric control equipment, which keeps the costs low. The coil is liquid cooled and produces a B(0) field of 0.95 T at 800 A. The field inhomogeneity in a cylindrical volume (diameter 5 mm, length 10 mm) is about 10 ppm, and the inductance is 190 microH. Switching times below 200 micros can be achieved. During 6 months of operation the coil has shown good stability and reliability.     

Laser heating of solid matter by light-pressure-driven shocks at ultrarelativistic intensities

The heating of solid targets irradiated by 5 x 10(20) W cm(-2), 0.8 ps, 1.05 microm wavelength laser light is studied by x-ray spectroscopy of the K-shell emission from thin layers of Ni, Mo, and V. A surface layer is heated to approximately 5 keV with an axial temperature gradient of 0.6 microm scale length. Images of Ni Ly(alpha) show the hot region has 100 G bar light pressure compresses the preformed plasma and drives a shock into the solid, heating a thin layer.