Versatile high-pressure gas apparatus for benchtop NMR: Design and selected applications.

A simple, yet highly versatile setup is presented for benchtop NMR analyses of gases at high-pressure. It consists mostly of commercial parts and includes multiple safety features while maintaining a small size to fit into a 1.20 m wide fume hood. Pressures up to 200 bar can be adjusted independently of the sample gas-bottle pressure in a matter of seconds. Mixtures of multiple gases can be produced in situ in a mixing chamber, which also serves to adjust the pressure. The high-pressure hardware and benchtop NMR spectrometer have been tested for long-term stability and repeatability of the measurements. The versatility of the setup is demonstrated by analyzing hydrocarbon-gas with attention to linewidths as well as their 1H relaxation times, by improving the resolution of 1H NMR spectra from solid polymers with pressurized CO2, and by visualizing the ingress of gaseous and supercritical methane into liquid benzene.

Selective magnetic resonance signal suppression by colored Frank excitation.

Inspired by the growing interest in miniaturized NMR devices and their applications in material science as well as in chemical and biological research, low power rf excitation is explored. 1H NMR spectra have been measured with low power Frank excitation and are compared to spectra obtained by single-pulse excitation. Frank excitation consists of a large number of phase-modulated, constant-amplitude rf-pulses. A Frank sequence is divided into packages of discrete phase wavelets that correspond to a scan across a spectral frequency range. The largely coherent excitation is found experimentally to require less power than white noise excitation. The package structure suggests that individual wavelets can be omitted to skip individual frequency regions in the excitation, converting the white Frank excitation into colored Frank excitation. This work explores different approaches of colored, selective Frank excitation for spectroscopy and imaging. It is motivated by the aim to eliminate the rf amplifier from the NMR spectrometer so as to enable further miniaturization of NMR instruments. Colored Frank excitation bears promise as a low-power modality for solvent signal suppression in spectroscopy and motion tagging in magnetic resonance imaging.

NMR relaxometry of oil paint binders.

Mobile nuclear magnetic resonance (NMR) is a flexible technique for nondestructive characterization of water in plants, the physical properties of polymers, moisture in porous walls, or the binder in paintings by relaxation measurements. NMR relaxation data report material properties and therefore can also help to characterize the state of tangible cultural heritage. In this work, we discuss the relaxation behavior in two series of naturally aged paint mock-up samples. First, paints with different pigment concentrations were prepared and investigated in terms of the longitudinal and transverse relaxation-time distributions. We document the evolution of both relaxation-time distributions during the initial drying stage and demonstrate the heightened importance of transverse over longitudinal relaxation measurements. Second, we observe nonlinear dependences of the relaxation times on the pigment concentration in a typical oil binder. Third, in a study of naturally aged paint samples prepared in the years between 1914 and 1951 and subsequently aged under controlled conditions, we explore the possibility of determining the age of paintings using partial least square regression (PLS) by fitting T1 -T2 data with the sample age. Our results suggest some correlation, albeit with significant scatter. Estimating the age of a painting stored under unknown conditions from NMR relaxation data is therefore not feasible, as the cumulative effects of light irradiation, humidity, and biological degradation further obfuscate the chemical and physical impact of aging on the relaxation times in addition to the impact of pigment concentration.

Elucidating the ionic liquid distribution in monolithic SILP hydroformylation catalysts by magnetic resonance imaging.

Monolithic silicon carbide supported ionic liquid-phase (SILP) Rh-catalysts have very recently been introduced for gas-phase hydroformylation as an important step toward industrial upscaling. This study investigates the monolithic catalyst system in combination with different impregnation procedures with non-invasive magnetic resonance imaging (MRI). The findings were supported by X-ray microtomography (micro-CT) data of the monolithic pore structure and a catalytic performance test of the catalyst system for 1-butene gas-phase hydroformylation. MRI confirmed a homogeneous impregnation of the liquid phase throughout the full cross-section of the cylindrical monoliths. Consistent impregnations from one side to the other of the monoliths were achieved with a stabilizer in the system that helped preventing inhomogeneous rim formation. External influences relevant for industrial application, such as long-term storage and temperature exposure, did not affect the homogeneous liquid-phase distribution of the catalyst. The work elucidates important parameters to improve liquid-phase catalyst impregnation to obtain efficient monolithic catalysts for industrial exploitation in gas-phase hydroformylation as well as other important industrial processes.

Continuous hyperpolarization with parahydrogen in a membrane reactor.

Hyperpolarization methods entail a high potential to boost the sensitivity of NMR. Even though the "Signal Amplification by Reversible Exchange" (SABRE) approach uses para-enriched hydrogen, p-H2, to repeatedly achieve high polarization levels on target molecules without altering their chemical structure, such studies are often limited to batch experiments in NMR tubes. Alternatively, this work introduces a continuous flow setup including a membrane reactor for the p-H2, supply and consecutive detection in a 1 T NMR spectrometer. Two SABRE substrates pyridine and nicotinamide were hyperpolarized, and more than 1000-fold signal enhancement was found. Our strategy combines low-field NMR spectrometry and a membrane flow reactor. This enables precise control of the experimental conditions such as liquid and gas pressures, and volume flow for ensuring repeatable maximum polarization.

Imaging of copper oxygenation reactions in a bubble flow.

Reactions of gases with liquids play a crucial role in the production of many bulk chemicals. Often, the gas is bubbled into the chosen reactor. Most of the processes at the gas-liquid interface of the bubbles and in their tails are not fully understood and warrant further investigation. For this purpose, NMR imaging or Magnetic Resonance Imaging has been applied to visualize some of the processes in the bubble tail. To generate sufficient contrast, a magnetogenic gas-liquid reaction associated with a change of magnetic state, from diamagnetic to paramagnetic, was employed. In this work, a copper(I)-based compound was oxidized to copper(II) to exploit relaxation contrast. To match the speed of the rising bubbles to the acquisition time of the spin-echo imaging sequence, polyethylene glycol was added to increase the viscosity of the reacting solution. Images of the oxygen ingress into a static solution as well as of oxygen bubbles rising in the solution are presented. In both cases, changes in magnetism were observed, which reported the hydrodynamic processes.

NMR and MRI of blood-dissolved hyperpolarized Xe-129 in different hollow-fiber membranes.

Magnetic resonance of hyperpolarized (129)Xe has found a wide field of applications in the analysis of biologically relevant fluids. Recently, it has been shown that the dissolution of hyperpolarized gas into the fluid via hollow-fiber membranes leads to bubble-free (129)Xe augmentation, and thus to an enhanced signal. In addition, hollow-fiber membranes permit a continuous operation mode. Herein, a quantitative magnetic resonance imaging and spectroscopy analysis of a customized hollow-fiber membrane module is presented. Different commercial hollow-fiber membrane types are compared with regard to their (129)Xe dissolution efficiency into porcine blood, its constituents, and other fluids. The presented study gives new insight into the suitability of these hollow-fiber membrane types for hyperpolarized gas dissolution setups.

Multiparametric high-resolution imaging of barley embryos by multiphoton microscopy and magnetic resonance micro-imaging.

Nonlinear optical microscopy and magnetic resonance imaging (MRI) address different properties of the sample and operate on different geometrical scales. MRI maps density and mobility of molecules tracking specific molecular signatures. Multiphoton imaging profits from the nonlinear absorption of light in the focus of a femtosecond laser source stimulating the autofluorescence of biomolecules. As this effect relies on a high light intensity, the accessible field of view is limited, but the resolution is very high (a few hundred nanometers). Here, we aim to link the different accessible scales and properties addressed in the different techniques to obtain a synoptic view. As model specimen we studied embryos of barley. Multiphoton stimulated autofluorescence images and images of second harmonic generation are achieved even down to low magnification (10x), low numerical aperture (N.A. 0.25) conditions. The overview images allowed morphological assignments and fluorescence lifetime imaging provides further information to identify accumulation of endogenous fluorophores. The second, complementary contribution from high-resolution MR images provides a 3D model and shows the embedding of the embryo in the grain. Images of the proton density were acquired using a standard 3D spin-echo imaging pulse sequence. Details directly comparable to the low magnification optical data are visible. Eventually, passing from the MR images of the whole grain via low magnification to high resolution autofluorescence data bridges the scale barrier, and might provide the possibility to trace transport and accumulation of, e.g., nutrients from large structure of the plant to the (sub-) cellular level.

Morphology and chain dynamics during collapse transition of PNIPAM gels studied by combined imaging, relaxometry and 129Xe spectroscopy techniques.

The temperature-induced shape transition of poly(N-isopropylacrylamide) gels of different cross-link densities was investigated by a combination of NMR techniques allowing the characterization of both the macroscopic collapse as well as the changes on a molecular scale related to the expulsion of water from the gel network. The proton-containing gel phase was visualized by swelling in heavy water, and the volume change was monitored by proton imaging for cross-link densities between 0.5% and 2.5%. Above the transition temperature of 35 degrees C, gel collapse led to a volume change of up to a factor of 17 for the gel of smallest cross-link density. Two spectral lines of 129Xe are found in the gel state and are assigned to the hydrophobic and hydrophilic parts of the network. In the collapsed state, the hydrophobic peak shows a strong shift while the hydrophilic peak disappears. A considerable shortening of both T1 and T2 of the gel protons upon collapse was found at a field of 4.7 T. At lower fields, the effect becomes more pronounced and qualitatively different dispersion behaviors between the swollen and the collapsed states are observed.

Environmental factors as delusional contents in patients with schizophrenia.

In a series of 50 consecutive cases in the outpatients' unit of Environmental Medicine (UEM) at the University Hospital of Aachen, Germany, five patients with the diagnosis of schizophrenia presented delusions of being poisoned by environmental factors. This case report illustrates the clinical features of the paranoid type of schizophrenic psychoses. Schizophrenia represents an important differential diagnosis in the interdisciplinary diagnosis and management of health problems attributed to environmental factors.

Working memory deficiencies in adults associated with low-level lead exposure: implications of neuropsychological test results.

BACKGROUND: Although lead exposure has steadily decreased in the last few years, some lead is still used in the metal processing industry, mostly for wall paints and plumbing. Recent studies on children showed neurobehavioral effects of low-level exposure, but little is known about the neurocognitive effects of lead concentrations in the upper reference range on adults. METHODS: The neuropsychological effects of lead exposure were examined in 39 adult outpatients at the Unit of Environmental Medicine (UEM), University Hospital, Aachen, Germany. All patients underwent a comprehensive medical examination, including psychiatric. Venous blood and urine samples were collected and tested for heavy metals and selenium. Since the neuropsychological examination was not expected to reveal any severe abnormalities, only specific attentiveness functions were analyzed (alertness, working memory, flexibility, intermodal comparison) since these areas were the likeliest to show objectifiable effects. The tests were conducted using a standardized computerized battery. RESULTS: Lead blood levels ranged from 1 to 65.6 microg/l (mean 27.4 +/- 16.2 microg/l). Although the neuropsychological test results of all patients were within the normal range, there were significant correlations between blood lead levels and the speed of information processing for working memory. CONCLUSIONS: The results indicate working memory dysfunctions in adults, the severity of which correlates directly with blood lead levels, supporting the hypothesis that increased blood lead levels can also be associated with measurable neurocognitive abnormalities.

[Different patterns of regional brain activation during emotional stimulation in alexithymics in comparison with normal controls]. / Differente Muster regionaler Hirnaktivität nach emotionaler Stimulation bei alexithymen Patienten im Vergleich zu Normalpersonen - Eine positronenemissionstomographische (PET-)Studie mit 15O-H2O und emotionaler Stimulierung durch autobiografische Erinnerung -

OBJECTIVE: This study was designed to determine patterns of regional brain activation during emotional stimulation in alexithymics as compared with normal controls. METHOD: We used 15O-water positron emission tomography and an emotional stimulation paradigm based upon autobiographic recall of either happy, sad or emotionally neutral situations. 10 normal subjects without medical or psychiatrical history were compared with 9 patients with somatoform disorder without any other DSM-IV diagnosis. TAS-20 was used as a measure for alexithymia, depression was measured using BDI. RESULTS: Normal controls showed significantly greater activation than alexithymics in cingulate areas, corpus callosum, and right superior and inferior frontal gyrus. Alexithymics activated significantly more in cuneus and precuneus, thalamus (pulvinar), left medial frontal, right inferior temporal, left superior temporal regions, left precentral gyrus, and the cerebellum. CONCLUSIONS: During emotional autobiographic recall, alexithymia, either trait or state, is characterized by utilization of different brain regions when compared to normal controls. The areas activated by alexithymic persons largely comprise of language related regions, leaving out limbic and paralimbic areas.