High-resolution liquid- and solid-state nuclear magnetic resonance of nanoliter sample volumes using microcoil detectors

The predominant means to detect nuclear magnetic resonance (NMR) is to monitor the voltage induced in a radiofrequency coil by the precessing magnetization. To address the sensitivity of NMR for mass-limited samples it is worthwhile to miniaturize this detector coil. Although making smaller coils seems a trivial step, the challenges in the design of microcoil probeheads are to get the highest possible sensitivity while maintaining high resolution and keeping the versatility to apply all known NMR experiments. This means that the coils have to be optimized for a given sample geometry, circuit losses should be avoided, susceptibility broadening due to probe materials has to be minimized, and finally the B(1)-fields generated by the rf coils should be homogeneous over the sample volume. This contribution compares three designs that have been miniaturized for NMR detection: solenoid coils, flat helical coils, and the novel stripline and microslot designs. So far most emphasis in microcoil research was in liquid-state NMR. This contribution gives an overview of the state of the art of microcoil solid-state NMR by reviewing literature data and showing the latest results in the development of static and micro magic angle spinning (microMAS) solenoid-based probeheads. Besides their mass sensitivity, microcoils can also generate tremendously high rf fields which are very useful in various solid-state NMR experiments. The benefits of the stripline geometry for studying thin films are shown. This geometry also proves to be a superior solution for microfluidic NMR implementations in terms of sensitivity and resolution.     

Stacked-ring electrostatic ion guide

In 1969 Bahr, Gerlich, and Teloy introduced an rf device that consisted of a stack of ring electrodes, with charge sign alternation between neighboring rings, to store or transport ions. Here we propose to operate such a device with electrostatic potentials rather than rf potentials: ions that move axially along the center of the guide are thereby subjected to an oscillating electrical potential similar to the sinusoidal rf potential in familiar rf-only multipole ion guides. The oscillating potential of the stacked-ring static ion guide focuses ions by exerting a field gradient force on the ions so as to push ions toward the central axis where the field is weakest. The stacked-ring ion guide produces an effectively static “pseudopotential” that is much steeper at the edge (potential varies as e ^r) compared to a quadrupole or octupole guide (for which the potential varies as r ² or r ⁶, where r is radial position) and that is much flatter near the center of the guide (for potentially higher ion flux). Advantages of the new ion guide include static rather than rf potential, low electrical noise, a large field-free region near the central axis of the guide, and simple mechanical construction. A disadvantage of the stacked-ring ion guide is that high ion axial kinetic energy is required; ions with axial kinetic energy that is too low may be trapped in the shallow pseudopotential well between adjacent ring electrodes.     

Application of pulsed field gradient NMR with high gradient strength for studies of self-diffusion in lipid membranes on the nanoscale

This work demonstrates the feasibility of noninvasive studies of lipid self-diffusion in model lipid membranes on the nanoscale using proton pulsed field gradient (PFG) NMR spectroscopy with high (up to 35 T/m) gradient amplitudes. Application of high gradients affords for the use of sufficiently small diffusion times under the conditions when the width of the gradient pulses is much smaller than the diffusion time. As a result, PFG NMR studies of partially restricted or anomalous diffusion in lipid bilayers become possible over length scales as small as 100 nm. This length scale is important because it is comparable to the size of membrane domains, or lipid rafts, which are believed to exist in biomembranes. In this work, high-gradient PFG NMR has been applied to study lipid self-diffusion in three-component planar-supported multibilayers (1,2-dioleoyl- sn-glycerol-3-phosphocholine/sphingomyelin/cholesterol). The degree of lipid orientation in the bilayers was determined with (31)P NMR. A special insert was designed to mechanically align the multibilayer stack at the magic angle with respect to the direction of the constant magnetic field to address the detrimental effects of proton dipole-dipole interactions on the NMR signal. This insert is an alternative to the conventional method of magic angle orientation of lipid membranes, the goniometer probe, which is not compatible with commercial high-gradient coils because of the lack of space in the magnet bore. Macroscopic orientation of the multibilayer stacks using the insert was confirmed with (1)H NMR spectroscopic studies and the comparison of results obtained from identical experiments using a goniometer probe for orientation. Diffusion studies were carried out at three different constant magnetic field strengths ( B 0) over a range of temperatures and diffusion times. The measured diffusivities were found to be in agreement with the data obtained previously by techniques that are limited to much larger length scales of diffusion observation than high-gradient PFG NMR.     

Trace analysis of glasses by magnetically enhanced rf GDMS

A radiofrequency (rf) glow discharge ion source coupled to a commercial double-focusing mass spectrometer was used for the direct trace element analysis of glass samples. By utilizing an additional ring-shaped magnet located behind the flat sample in an rf glow discharge ion source compared with a configuration without a magnet, the sputtering and ionization efficiency of glass samples was enhanced and the detection power for trace elements was improved. The detection limits for elements determined by rf glow discharge mass spectrometry at low mass resolution (m/Δm = 300) are 10–100 ng/g. Possible interferences of atomic ions of analyte and molecular ions which limited the determination of some elements (e.g. Ti, Mn, Fe, Ni, Co, Cu, Zn) could be resolved at the mass resolution of m/Δm = 3000. The detection limits for these elements were found to be about 100 ng/g. Relative sensitivity factors (RSFs) for all elements of interest with respect to Sr (internal standard element) were determined in the range of 0.2–3.     

Anode Magnetron Enhanced DC Glow Discharge Processes for Plasma Surface Cleaning and Polymerization

The objective of this study was to examine some fundamental factors involved in the design and construction of the anode magnetron dc glow discharge processes as well as its performance in plasma cleaning and polymerization. Those advantages of anode magnetron include the capability of the magnetron to operate at low pressure, as well as decreasing the thickness of cathode dark space, i.e., the negative glow which contains a higher concentration of ions and active species was more closely to the cathode surface, which makes the plasma surface cleaning and polymerization an effective and uniform processes. The deposition rate at a given discharge power is increased by the presence of anode magnetrons, and is also much higher relative to rf and af. The refractive index of dc plasma film at a given polymer thickness (such as TMS, 70 nm, RI: 2.4) is higher than rf, af, and cascade arc plasma (RI: 1.6–1.7).     

Fast numerical design of spatial-selective rf pulses in MRI using Krotov and quasi-Newton based optimal control methods

The use of increasingly strong magnetic fields in magnetic resonance imaging (MRI) improves sensitivity, susceptibility contrast, and spatial or spectral resolution for functional and localized spectroscopic imaging applications. However, along with these benefits come the challenges of increasing static field (B(0)) and rf field (B(1)) inhomogeneities induced by radial field susceptibility differences and poorer dielectric properties of objects in the scanner. Increasing fields also impose the need for rf irradiation at higher frequencies which may lead to elevated patient energy absorption, eventually posing a safety risk. These reasons have motivated the use of multidimensional rf pulses and parallel rf transmission, and their combination with tailoring of rf pulses for fast and low-power rf performance. For the latter application, analytical and approximate solutions are well-established in linear regimes, however, with increasing nonlinearities and constraints on the rf pulses, numerical iterative methods become attractive. Among such procedures, optimal control methods have recently demonstrated great potential. Here, we present a Krotov-based optimal control approach which as compared to earlier approaches provides very fast, monotonic convergence even without educated initial guesses. This is essential for in vivo MRI applications. The method is compared to a second-order gradient ascent method relying on the Broyden-Fletcher-Goldfarb-Shanno (BFGS) quasi-Newton method, and a hybrid scheme Krotov-BFGS is also introduced in this study. These optimal control approaches are demonstrated by the design of a 2D spatial selective rf pulse exciting the letters "JCP" in a water phantom.     

Langmuir probe characteristics in RF glow discharges

The current-voltage characteristics of Langmuir probes in rf glow discharges can be misinterpreted by the effects of rf time averaging, ionization near a probe, and expansion of the probe sheath. This paper presents a new Langmuir probe technique which can be used to determine the plasma parameters in rf glow discharges. Simple expressions for the time averaged I-V characteristics are derived for the cases of fully sinusoidal and partially rectified plasma potential waveforms. Examples of corresponding I-V characteristics obtained from argon rf glow discharges are also illustrated.     

Langmuir probe measurements of axial variation of plasma parameters in 27.1 MHz rf oxygen planar discharges

Langmuir probe studies have been performed on rf (27.1 MHz) discharges in O₂ under planar reactor conditions to determine the axial variation of the plasma parameters (positive ion density, electron temperature, and dc space potential) as a function of pressure (20–220 Pa) and power (10–150 W) or current (0.1–2 A). By monitoring the second derivative of the I–V probe characteristics, the suppression of the rf component in the probe circuit can be optimized. Referring to this problem, numerical studies provide relations for the determination of the residual rf component as well as of the dc component of the plasma potential at incomplete rf compensation. The positive ion density is obtained from the ion saturation currents. Here the effect of collisions between ions and neutral particles within the probe sheath (for p> 100 Pa) is considered. The electron energy distribution function is found to be of the Maxwellian type for all discharge conditions investigated here. If the pressure and the power exceed critical values, the axial charge carrier distribution is characterized by a valley formation in the bulk plasma center. This fact demonstrates that secondary electron emission due to ion impact on the electrode surfaces and following ionization by these electrons near the sheaths in front of the electrodes are significant processes for sustaining the discharge. At low pressures (p60 Pa) the dc plasma potential was found to be identical with the half-peak maintaining voltage of the discharge, in agreement with the model idea of a symmetric rf planar discharge where the rf voltage drop across the bulk plasma can be neglected. For growing pressure, however, the plasma system moves gradually toward a situation where the V-I characteristics of the discharge are significantly controlled by processes in the bulk plasma. This transition depends on the current density.     

Excitation of Radial Ion Motion in an rf-Only Multipole Ion Guide Immersed in a Strong Magnetic Field Gradient

Radiofrequency (rf) multipole ion guides are widely used to transfer ions through the strong magnetic field gradient between source and analyzer regions of external source Fourier transform ion cyclotron resonance mass spectrometers. Although ion transfer as determined solely by the electric field in a multipole ion guide has been thoroughly studied, transfer influenced by immersion in a strong magnetic field gradient has not been as well characterized. Recent work has indicated that the added magnetic field can have profound effects on ion transfer, ultimately resulting in loss of ions initially contained within the multipole. Those losses result from radial ejection of ions due to transient cyclotron resonance that occurs when ions traverse a region in which the magnetic field results in an effective cyclotron frequency equal to the multipole rf drive frequency divided by the multipole order (multipole order is equal to one-half the number of poles). In this work, we describe the analytical basis for ion resonance in a rf multipole ion guide with superposed static magnetic field and compare with results of numerical trajectory simulations.     

Permanent magnet assembly producing a strong tilted homogeneous magnetic field: towards magic angle field spinning NMR and MRI

We introduce a cylindrical permanent magnet design that generates a homogeneous and strong magnetic field having an arbitrary inclination with respect to the axis of the cylinder. The analytical theory of 3 D magnetostatics has been applied to this problem, and a hybrid magnet structure has been designed. This structure contains two magnets producing a longitudinal and transverse component for the magnetic field, whose amplitudes and homogeneities can be fully controlled by design. A simple prototype has been constructed using inexpensive small cube magnets, and its magnetic field has been mapped using Hall and NMR probe sensors. This magnet can, in principle, be used for magic angle field spinning NMR and MRI experiments allowing for metabolic chemical shift profiling in small living animals.     

Isocratic and gradient elution chromatography: a comparison in terms of speed, retention reproducibility and quantitation

Chromatographers are cautioned to avoid gradient elution when isocratic elution will do. In this work, we compared the analytical properties of gradient and isocratic separations of a sample which can be done quite readily under isocratic conditions. We found that gradient elution gave a shorter overall analysis with similar resolution of the critical pair compared to isocratic elution without sacrificing repeatability in retention time, peak area and peak height or linearity of the calibration curve. We also obtained acceptable repeatability in peak area/height and linearity of calibrations curves for a sample that required gradient elution using a practical baseline subtraction technique. Based on these results and related work which show that columns can be reequilibrated by flushing with less than two column volumes of the initial eluent, we conclude that many of the reasons given to avoid gradient elution deserve serious reconsideration, especially for those samples which are easily separated isocratically. However, we believe isocratic elution will remain preferable when: (1) the sample contains less than 10 weakly retained components (i.e. the last peak elutes with k' < 5) or (2) the gradient baseline impedes trace analysis.     

Two-photon Lee-Goldburg nuclear magnetic resonance: Simultaneous homonuclear decoupling and signal acquisition

We present NMR signals from a strongly coupled homonuclear spin system, (1)H nuclei in adamantane, acquired with simultaneous two-photon excitation under conditions of the Lee-Goldburg experiment. Small coils, having inside diameters of 0.36 mm, are used to achieve two-photon nutation frequencies of approximately 20 kHz. The very large rf field strengths required give rise to large Bloch-Siegert shifts that cannot be neglected. These experiments are found to be extremely sensitive to inhomogeneity of the applied rf field, and due to the Bloch-Siegert shift, exhibit a large asymmetry in response between the upper and lower Lee-Goldburg offsets. Two-photon excitation has the potential to enhance both the sensitivity and performance of homonuclear dipolar decoupling, but is made challenging by the high rf power required and the difficulties introduced by the inhomogeneous Bloch-Siegert shift. We briefly discuss a variation of the frequency-switched Lee-Goldburg technique, called four-quadrant Lee-Goldburg (4QLG) that produces net precession in the x-y plane, with a reduced chemical shift scaling factor of 13.     

Development of modulated rf sequences for decoupling and recoupling of nuclear-spin interactions in sample-spinning solid-state NMR: application to chemical-shift anisotropy determination

An approach to design modulated rf sequences under sample spinning which decouple/recouple a specific nuclear-spin interaction in solid-state NMR is presented. The Euler angles of the spin rotation caused by a general rf field are forced to fulfill the symmetry principle theory for selecting an interaction of interest. Then, modulated rf sequences are directly obtained from the Euler angles with a large degree of freedom. rf sequences with high performance can be selected from them by numerically optimizing rf sequence parameters. As an example of this approach, an amplitude- and phase-modulated rf sequence to recouple chemical-shift anisotropy (CSA) is developed, which is robust with respect to rf inhomogeneity. Two-dimensional (2D) experiments with this rf sequence under on and off magic-angle spinning (MAS) provide one-dimensional and 2D powder patterns, respectively. The latter enables us to determine the CSA principal values more accurately even for overlapped signals in MAS spectra. The effectiveness of this modulated rf sequence is experimentally demonstrated on [(15)N]-N-acetyl-D,L-alanine for determination of the (15)N and (13)CO CSA principal values.     

Simple procedure for the fabrication of flexible NMR shim coils

Photolithography allows simple fabrication of flexible NMR shim coils. Here we demonstrate this procedure by fabricating optimized first-order shim coils for a transverse field orientation “Halbach” permanent magnet cylinder.     

New hardware for radio frequency powered glow discharge spectroscopies and its capabilities for analytical applications

A new radio frequency (rf) hardware is developed for glow discharge spectroscopic methods. The resulting features and its capabilities for analytical applications are discussed. The electrical equipment developed allows to work as quickly, stably, reliably and easily as known from the direct current (dc) mode. Moreover, the rf power measurement has been improved. The hardware has been developed, optimised and tested for glow discharge optical emission spectroscopy (GDOES), but nevertheless it is possible to use it for all procedures applying glow discharge sources.     

New hardware for radio frequency powered glow discharge spectroscopies and its capabilities for analytical applications

A new radio frequency (rf) hardware is developed for glow discharge spectroscopic methods. The resulting features and its capabilities for analytical applications are discussed. The electrical equipment developed allows to work as quickly, stably, reliably and easily as known from the direct current (dc) mode. Moreover, the rf power measurement has been improved. The hardware has been developed, optimised and tested for glow discharge optical emission spectroscopy (GDOES), but nevertheless it is possible to use it for all procedures applying glow discharge sources.     

First signal on the cryogenic fourier-transform ion cyclotron resonance mass spectrometer

The construction and achievement of the first signal on a cryogenic Fourier-transform ion cyclotron resonance mass spectrometer (FTICR-MS) are reported here, demonstrating proof-of-concept of this new instrument design. Building the FTICR cell into the cold bore of a superconducting magnet provided advantages over conventional warm bore design. At 4.2 K, the vacuum system cryopumps itself, thus removing the requirement for a large bore to achieve the desired pumping speed for maintaining base pressure. Furthermore, because the bore diameter has been reduced, the amount of magnet wire needed to achieve high field and homogeneity was also reduced, greatly decreasing the cost/Tesla of the magnet. The current instrument implements an actively shielded 14-Tesla magnet of vertical design with an external matrix-assisted laser desorption/ionization (MALDI) source. The first signal was obtained by detecting the laser desorbed/ionized (LDI) C(60)(+*) ions, with the magnet at 7 Tesla, unshimmed, and the preamplifier mounted outside of the vacuum chamber at room temperature. A subsequent experiment done with the magnet at 14 Tesla and properly shimmed produced a C(60) spectrum showing approximately 350,000 resolving power at m/z approximately 720. Increased magnetic field strength improves many FTMS performance parameters simultaneously, particularly mass resolving power and accuracy.     

Construction and Evaluation of a LEGO Spectrophotometer for Student Use

A simple visible-wavelength spectrophotometer has been constructed for educational purposes. The spectrophotometer contains simple, inexpensive components students can easily work with (small flashlight bulbs, batteries, etc.) and uses LEGO pieces for construction of the optical support elements. The spectrophotometer was designed to give students hands-on experience with typical spectrophotometer modules so that they may understand the important stages in the design of a scientific instrument. The spectrophotometer was characterized by examining an absorption spectrum and calibration curves of potassium permanganate.     

Probing the pH-dependent chain dynamics of poly(acrylate acid) in concentrated solution by using a cationic AIE fluorophore

We report a novel strategy to study the chain dynamics of poly(acrylic acid) (PAA) in a relative concentrated solution (1.0 g/L). The strategy is based on the fluorescent probe (DCTPE) with unique aggregation-induced emission (AIE) characteristics. Free DCTPE molecules are non-emissive in aqueous solution, but they become highly emissive when trapped in polymer coils. The fluorescence intensity is proportional to the efficiency of trapping DCTPE molecules in polymer coils. By correlation the change of fluorescence intensity with the variation of pH value (from 1.78 to 12.06), the PAA chain’s dynamics in the relatively concentrated solution have been elucidated into three processes. In the pH range from 12.06 to 6.0, PAA chains take an extended and non-folding conformation. Changing pH from 6.0 to 3.86, PAA chains are partially protonated and loosely packed polymer coils are formed. Further lowering the pH value of the solution (from 3.86 to 1.78), protonated segments dominate the PAA chains, and at the same time, the intermolecular hydrogen bonding takes effect, thus the polymer chains posses in the conformation of more compact coils.     

Optimization of an rf-powered magnetron glow discharge for the trace analysis of glasses and ceramics

A radiofrequency (rf) powered planar magnetron glow discharge ion source has been designed and coupled to a double-focusing mass spectrometer. Superposition of the electrical field of the plasma in the cathode dark space and the magnetic field obtained from a ring-shaped magnet located directly behind the sample (cathode) form the electron traps and enhance the sputtering and ionization efficiency of the ion source. In order to establish optimum conditions for the trace analysis of nonconducting materials, mass spectrometric studies have been carried out on the ion signal intensities and energy distributions of analyte and discharge gas ions depending on pressure.