Transfer of1H and13C dynamic nuclear polarization from immobilized nitroxide radicals to flowing liquids

In this study,¹H and¹³C dynamic nuclear polarization (DNP) was generated at a magnetic field strength of 0.33 T utilizing silica phase immobilized nitroxide (SPIN) samples. The polarization was subsequently transferred to flowing liquids and monitored at a magnetic field strength of 4.7 T. These solid/liquid intermolecular transfer (SLIT) experiments provide efficient polarization transfer without the necessity of the free radical system present in the monitoring fluid. Specifically, ultimate¹H SLIT DNP Overhauser enhancements of ?56 and ?110 have been observed for benzene and chloroform in the presence of SPIN system 2, respectively. The¹³C SLIT DNP enhancement for benzene is dominated by three-spin effects and poor leakage factors (f _c). However, a particularly favorable case is the chloroform/SPIN 2 system which exhibits a scalar dominated enhancement. For this case, positive enhancements 40–60 times the¹³C thermal Boltzmann magnetization at 4.7 T have been observed. The large scalar dominated¹³C DNP enhancement for this system represents one of the largest experimental enhancements reported to date. The¹³C DNP spectra for other samples which exhibit favorable scalar¹³C dominated enhancements (e.g., Freon 113) are also presented. Three different SPIN systems were also prepared and characterized in the present study.     

Intermolecular interactions of benzene and carbon tetrachloride with selected free radicals in solution as studied by 13C and 1H dynamic nuclear polarization

Intermolecular hyperfine coupling between ¹³C nuclei and free-radical unpaired electron spins has been examined for six combinations of three free radicals and two solvent molecules. From magnetic field and temperature-dependent dynamic nuclear polarization measurements, scalar and dipolar coupling contributions have been separated. Interpretation of these results in terms of a modified diffusion model revealed scalar spectral density functions with two or three frequency components, each characterized by a distinct contact time. Collisions with the shortest time constant were found to be nearly independent of the system and accounted for approximately 90 per cent of all radical-receptor collisions and 30 per cent of the scalar relaxation rate. These have been related to random elastic collisions. In contrast, collisions with long contact times were found to be highly system dependent. Although few in number, they accounted for a relatively large fraction of the scalar relaxation rate because of their long duration. These have been interpreted as stereospecific collisions which reflect the tendency of the colliding partners to form weak transient complexes. Lastly, relative scalar coupling energies were obtained and related to the availability of the unpaired electron and to the structure of both colliding molecules.     

A.C. electrical conductivity of pure and doped potassium perchlorate

A.C. electrical conductivity of potassium perchlorate (KP) has been measured in the temperature range 25–325°C at frequencies ranging from 50–500 Hz using an automated technique. The results are interpreted in terms of a novel mechanism involving Schottky defects in the anion sublattice and Frenkel defects in the cation sublattice. The conductivity behavior of KP is compared with literature data on similar low-symmetry systems containing polyatomic ions.     

1H and13C nuclear magnetic relaxation and local dynamics of lysozyme and synthetic polypeptides

The combined analysis of¹H and¹³C NMR relaxation data in solid lysozyme and some typical homopolypeptides was carried out by using “model-free” approach. Three types of relaxation transitions (γ’, γ and β) were revealed in the temperature range investigated. The microdynamical parameters of these motions were determined. From the comparison of these parameters with those of selected synthetic polymers it follows that the molecular motions in proteins and synthetic polymers are of the same nature. All these motions show pronounced anisotropic character. In the investigated temperature range no molecular motions corresponding to α-relaxation (liquid-like) transition were revealed. The hydration effects on parameters of the motions in proteins were considered. The most pronounced effect takes place for β-transition. The effect of Brownian rotation of protein molecule in solution on measured correlation function of local motions was also discussed.     

Field-cycling NMR investigations of (13)C-(1)H cross-relaxation and cross-polarisation: the nuclear solid effect and dynamic nuclear polarisation

A field-cycling NMR investigation of (1)H-(13)C polarisation transfer using cross-relaxation and the nuclear solid effect (NSE) is described. Dynamic nuclear polarisation (DNP) of the (13)C spins is observed when forbidden transitions are driven by r.f. irradiation at the sum and difference Larmor frequencies of the two nuclei. When the (1)H spins are pre-polarised, a significant transfer of polarisation to the (13)C nuclei is achieved in a time short compared with the spin-lattice relaxation time of (13)C. The cross-polarisation arising from the NSE is studied as a function of B-field and time. These results are compared with the solutions of the differential equations that govern the coupled system of (1)H-(13)C spins. The effects of cross-relaxation are incorporated into the model for the first time and good agreement between theory and experiment is obtained. The experiments have been conducted at 20K on a (13)C-enriched sample of benzoic acid.     

1H and 13C NMR Determination of 1-Naphtyl-Polymethoxylated Diphenylwiethanes

The complete structural analysis of 1-[(4-methoxyphenyl)-(3,4,5-trimethoxyphe- nyl)methyl]naphtalene 5a and 1-[(2,5-dimethoxyphenyl)-(3,4,5-trimethoxyphenyl) methyljnaphtalene 5b, prepared by alkylation of 1-[chloro-(3,4,5-trimethoxyphenyl) methyl]naphtalene without by-products such as benzofluorene 2, may be accurately determined by ¹H, ¹³C NMR and 2D NMR analysis.     

1H and 13C NMR studies of molecular dynamics in the biocopolymer of glycolide and epsilon-caprolactone

Copolymers of glycolide and epsilon-caprolactone were studied using differential scanning calorimetry and solid-state NMR. The variation of the T1 relaxation time with temperature reflects local disorder and can be quantified in terms of the distribution of correlation times predicted by the Davidson-Cole model. T, relaxation is dominated by trans-gauche isomerisation, with an activation energy of 34-35 kJ mol(-1).     

Dynamic tunneling polarization as a quantum rotor analogue of dynamic nuclear polarization and the NMR solid effect

The populations of the tunneling states of CH(3) are manipulated by rf irradiation of weakly allowed sideband transitions within the manifold of tunneling-magnetic levels. Substantial positive and negative CH(3) tunneling polarizations are observed, providing a quantum rotor analogue of dynamic nuclear polarization and the solid effect in NMR. The field-cycling NMR technique used in the experiments employs level crossings between tunneling and Zeeman systems to report on the tunneling polarization. The tunneling lifetimes are measured and the field dependence investigated.     

A low-temperature thermometer for 1H, 19F,and 13C

A single sample is described which can be used with either proton, fluorine, or carbon resonance spectra to calibrate probe temperature down to -145°C. Calibration data are tabulated.     

雪胆素C的1H和13C NMR化学位移完全归属

雪胆素C是一个雪胆素甲在碱性条件下，乙酰基转移产生的同分异构体. 文中报道了应用¹³C NMR-DEPT、¹H-¹H COSY, NOESY, ¹³C-¹H COSY等多种NMR技术，对雪胆素C的NMR碳氢化学位移完全指定.     

1H and 13C NMR studies of glycine in anisotropic media: double-quantum transitions and the effects of chiral interactions

The (1)H NMR spectrum of glycine in stretched gelatin gel and in cromolyn liquid crystal displays a well-resolved doublet due to (1)H-(1)H dipolar interaction. Multiple spectra were obtained within a wide range of offset frequencies of partially saturating radio-frequency (RF) radiation to generate steady-state irradiation envelopes or z-spectra of glycine. Maximal suppression of the doublet occurred when the irradiation was applied exactly at the centre frequency, between the two glycine peaks. This phenomenon is due to double-quantum transitions and is similar to our previous work on quadrupolar nuclei (2)H (HDO) and (23)Na(+). When the (13)C isotopomer glycine-2-(13)C was used, the same effect was found in twice, split by (1)J(CH)+2D(CH). Additional signals in (1)H and (13)C NMR due to prochiral-chiral interactions were found when glycine-2-(13)C was dissolved in chiral anisotropic gelatin and κ-carrageenan gels. The NMR spectra were successfully simulated assuming a (2)J(HH) coupling constant of -16.5Hz and two distinct dipolar coupling constants for the -(13)CH(2)- group (D(C,HA), and D(C,HB)).     

Conductivity and optical studies of plasticized solid polymer electrolytes doped with carbon nanotube

Solid polymer electrolyte films based on Poly(ethylene oxide) (PEO) complexed with lithium hexafluorophosphate (LiPF₆), ethylene carbonate (EC) and amorphous carbon nanotube (αCNTs) were prepared by the solution cast technique. The conductivity increases from 10^?10 to 10^?5 Scm^?1 upon the addition of salt. The incorporation of EC and αCNTs to the salted polymer enhances the conductivity significantly to 10^?4 and 10^?3 Scm^?1. The complexation of doping materials with polymer were confirmed by X-ray diffraction and infrared studies. Optical properties like direct band gap and indirect band gap were investigated for pure and doped polymer films in the wavelength range 200–400 nm. It was found that the energy gaps and band edge values shifted to lower energies on doping.     

1H-13C polarization transfer in membranes: a tool for probing lipid dynamics and the effect of cholesterol

Phospholipid bilayers with over 20% cholesterol can form a liquid-ordered (l(o)) phase, which can be found in lateral domains, called rafts, in biomembranes. We show here that high-resolution (13)C and (1)H solid-state NMR are well suited to explore this phase, intermediate between gel and fluid. This approach can be applied to artificial or natural membranes, with no isotopic enrichment and with the help of magic-angle spinning (MAS), taking advantage of the high resolution and sensitivity of these nuclei. The sensitivity of magnetization transfer schemes to different lipid states has allowed us here to discriminate between various phases. We show that the phase composed of unsaturated phospholipids and cholesterol differs, in terms of lipid dynamics, both from the previously described l(o) phase and from the liquid-disordered phase.     

Preservation of endometallofullerene La@C82 in polycarbonate: EPR, ENDOR, and NMR studies

On embedding in poly(bisphenol A carbonate) film, La@C₈₂ has featured the exclusive stability against oxygen for more than 1 year's storage of the polymer films on air. The EPR spectral parameters of La@C₈₂ have occurred to be sensitive to the segmental mobility and the phase transition of the polymer from the glassy to the high-elasticity state. Furthermore, the intense matrix ¹H-electron nuclear double resonance (ENDOR) signal discovered in this system testifies the partial transfer of the electron spin density outside the fullerene cage onto the polymer protons. The ¹³⁹La NMR spectrum of the same suggests that La@C₈₂ forms nanoparticles, in which the metal atoms strongly interact with the delocalized electrons. The “spin-leakage” of the fullerene shell, along with the tendency of endohedral fullerenes (EMF) to form nanoparticles, is worth consideration in sight of their applications in material sciences.     

Theoretical treatment of pulsed Overhauser dynamic nuclear polarization: Consideration of a general periodic pulse sequence

A general theoretical approach to pulsed Overhauser-type dynamic nuclear polarization (DNP) is presented. Dynamic nuclear polarization is a powerful method to create non-thermal polarization of nuclear spins, thereby enhancing their nuclear magnetic resonance signals. The theory presented can treat pulsed microwave irradiation of electron paramagnetic resonance transitions for periodic pulse sequences of general composition. Dynamic nuclear polarization enhancement is analyzed in detail as a function of the microwave pulse length for rectangular pulses and pulses with finite rise time. Characteristic oscillations of the DNP enhancement are found when the pulse-length is stepwise increased, originating from coherent motion of the electron spins driven by the pulses. Experimental low-field DNP data are in very good agreement with this theoretical approach.