A. Woźniak-Braszak

High homogeneity B1 30.2 MHz Nuclear Magnetic Resonance Probe for off-resonance relaxation times measurements

This paper reports on design and construction of a double coil high-homogeneity ensuring Nuclear Magnetic Resonance Probe for off-resonance relaxation time measurements. NMR off-resonance experiments pose unique technical problems. Long irradiation can overheat the sample, dephase the spins because of B(1) field inhomogeneity and degrade the signal received by requiring the receiver bandwidth to be broader than that needed for normal experiment. The probe proposed solves these problems by introducing a separate off-resonance irradiation coil which is larger than the receiver coil and is wound up on the dewar tube that separates it from the receiver coil thus also thermally protects the sample from overheating. Large size of the irradiation coil also improves the field homogeneity because as a ratio of the sample diameter to the magnet (coil) diameter increases, the field inhomogeneity also increases (Blümich et al., 2008) [1]. The small receiver coil offers maximization of the filling factor and a high signal to the noise ratio.

The Instrument Set for Generating Fast Adiabatic Passage

The design and construction of a high-performance, low-cost, and easy to assemble adiabatic extension set for homebuilt and commercial spectrometers is described. Described apparatus set was designed for the fast adiabatic passage generation and is based on direct digital synthesizer DDS. This solution gives generator high signal to noise ratio, phase stability even during frequency change which is only possible in expansive commercial high-end hardware. Critical synchronization and timing issues are considered and solutions are discussed. Different experimental conditions and techniques for the measurements are briefly discussed. The proposed system is very flexible and might be used for the measurement of low-frequency nuclear magnetic resonance.

Effect of fullerene derivates on thermal and crystallization behavior of PBT/decylamine-C 60 and PBT/TCNEO-C 60 nanocomposites

The paper describes the process of the preparation of new nanocomposites based on poly(butylene terephthalate) and C60 nanoparticles modified by decylamine (DA) and tetracyanoethylene oxide (TCNEO), respectively. Thermal and crystallization properties of new synthesized nanocomposites were investigated by means of thermal differential scanning calorimetry (DSC). The experimental results demonstrate the effect of fullerene derivates, DA-C60 and TCNEO-C60, on the melting and crystallinity processes of nanocomposites. The morphology of new nanocomposites was investigated by SEM.

Methodology for solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems

This work presents the theoretical analysis of cross-relaxation and its applications to the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. The solid state NMR experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively. It is worth noting that this spectrometer includes a specially designed probe which simultaneously works at two slightly differing frequencies for protons and fluorine nuclei with complete absence of their interference. Contrary to a large number of previous cross-relaxation studies, in our experiments proton spins can be polarized in the magnetic field B0 or excited by rf pulses, while fluorine spins are continuously saturated for a long time. The saturation of fluorines is maintained throughout the whole duration of the experiment. It leads to a simplification of the mathematical analysis of the experimental results.

Molecular dynamics of poly(ethylene 2,6-naphthalate)-polycarbonate composite by nuclear magnetic resonance

The aim of the work was to examine molecular dynamics of a series of poly(ethylene 2,6-naphthalate)-polycarbonate blends with changing weight ratio of copolymers by off-resonance nuclear magnetic resonance technique. It was shown that this technique provides information about the correlation times of the internal motions. The spectral density function amplitudes were estimated on the basis of the dispersion of the spin-lattice relaxation time off-resonanceTlpoff. The measurements were performed for two series of blends which had been injection moulded with and without compatibilizer. The new polymer materials were also characterized using differential scanning calorimetry. Samples obtained after injection moulding and annealing became amorphous, which indicates that a reaction of transesterification process between the two polymers occurred.

Methodology for solid state NMR off-resonance study of molecular dynamics in heteronuclear systems

Methodology for the study of dynamics in heteronuclear systems in the laboratory frame was described in the previous paper [1]. Now the methodology for the study of molecular dynamics in the solid state heteronuclear systems in the rotating frame is presented. The solid state NMR off-resonance experiments were carried out on a homemade pulse spectrometer operating at the frequency of 30.2 MHz for protons. This spectrometer includes a specially designed probe which contains two independently tuned and electrically isolated coils installed in the coaxial position on the dewar. A unique probe design allows working at three slightly differing frequencies off and on resonance for protons and at the frequency of 28.411 MHz for fluorine nuclei with complete absence of their electrical interference. The probe allows simultaneously creating rf magnetic fields at off-resonance frequencies within the range of 30.2-30.6 MHz and at the frequency of 28.411 MHz. Presented heteronuclear cross-relaxation off-resonance experiments in the rotating frame provide information about molecular dynamics.

Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems.

The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2MHz and 28.411MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins (1)H are polarized in the magnetic field B0 while fluorine spins (19)F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.

Local motions in poly(ethylene-co-norbornene) studied by 1H NMR relaxometry

Molecular motions in poly(ethylene-co-norbornene) were studied in a temperature range well below its glass transition point by a few techniques based on the NMR phenomenon. Temperature dependencies of proton spin-lattice relaxation times T1 (at 200 MHz and at 30.2 MHz), proton spin-lattice relaxation time in the rotating frame T1ρ (at 68 kHz) and frequency dispersion of proton spin-lattice off-resonance relaxation times in the rotating frame T1ρ(off) were determined for the copolymer. Analysis of (1)H NMR relaxation data permitted characterization of local motions occurring in the copolymer i.e. rotation of methyl groups around C3 axes, reorientations of methylene groups and motions of segments of polymer chains including norbornene groups.

Study of cross - relaxation and molecular dynamics in the solid 3-(trifluoromethyl) benzoic acid by solid state NMR off - resonance

Molecular dynamics of the solid 3-(trifluoromethyl) benzoic acid containing proton 1H and fluorine 19F nuclei was explored by the solid-state NMR off - resonance technique. Contrary to the previous experiments the proton nuclei system I relaxed in the off - resonance effective field B→e while fluorine nuclei system S was saturated for short time in comparison to the relaxation time T1I. New cross - relaxation solid - state NMR off - resonance experiments were conducted on a homebuilt pulse spectrometer operating at the on-resonance frequency of 30.2MHz, at the off - resonance frequency varied between 30.2 and 30.6MHz for protons and at the frequency of 28.411MHz for fluorines, respectively. Based on the experimental data the dispersions of the proton off - resonance spin - lattice relaxation rate ρρI, the fluorine off - resonance spin - lattice relaxation rate ρρS and the cross - relaxation rate σρ in the rotating frame were determined.

Structure and Internal Dynamics of Acid K Salt of (E)-2-hydroxyimino-2-cyanoacetic Acid Ethyl Ester

Abstract An investigation of the internal dynamic of molecular groups existing in a molecule of acid K salt of (E)-2-hydroxyimino-2-cyanoacetic acid ethyl ester is the subject of the work. Using the NMR method we could find such types of motions which could well describe the experimental temperature dependences of spin lattice relaxation time, and the second moment of experimental 1H NMR line. Those techniques of the 1H NMR method allow one to draw conclusions on activation parameters of following motions: reorientation of methyl group, reorientation of ethyl group, H jump in the hydrogen bond bridge, anisotropic (axial) reorientation of the whole molecule around O⋯H–O chemical bonds.