Biaxial nematic phase in a thermotropic liquid-crystalline side-chain polymer

We report on variable-angle deuterium NMR measurements of nematic liquid-crystalline side-chain polymers, where we have found proof of the existence of a biaxial nematic phase in a system with a side-on attachment of the mesogenic group to the polymer backbone. This provides efficient coupling to the polymer backbone and thus stabilizes the as yet elusive biaxial phase. The experimental approach is validated on a uniaxial end-on nematic polymer, and the reliability of the results is investigated in detail using two-dimensional correlation spectra, providing information on director distribution effects.     

Study of fast switching processes due to electric and magnetic fields-an NMR approach

Solid state NMR techniques have been developed to investigate dynamic molecular effects (e.g., molecular reorientations) due to simultaneously applied external electric fields on electrically sensitive materials such as liquid crystals (LC), liquid crystalline polymers (LCP) and polymeric electrets. Such effects can be observed only on relatively thin systems (10-200 μm). That means that many scans are necessary to achieve a sufficiently high signal-to-noise-ratio in the spectra (500-1000 scans). If the material is also magnetically sensitive, the electric field can be used to orient molecules in a starting orientational state and by switching-off the voltage to access fast reorientation processes in the magnetic field B₀. Until now, the behaviour of orientable molecular systems under the influence of electric fields has been investigated by means of a more or less quasistatic approach (LCP: 100 V, electrets: 1 kV) in equilibrium states. The achievable time resolution depends on the desired signal-to-noise-ratio. For the case of proton NMR this means a time resolution of about 10 min. However, very often switching processes occur on a much shorter time scale. Using conventional techniques it is impossible to observe fast (ca. 100 μs) electrically or magnetically induced reorientation processes. In this work, we present a concept to overcome the problems outlined above and to extend the area of our current in situ NMR investigations on thin electrically-switched or poled polymeric layers. The basic idea is to include synchronized electric pulses during the NMR experiment using the preparation and/or mixing periods of a 1D or 2D pulse sequence for the application of an orienting field (electric or magnetic) and to use the reversibility of the molecular switching phenomenon to achieve a sufficient signal-to-noise-ratio. The techniques extend the range of possible investigations from about 100 μs to approximately T₁ for correlated spectra (and to longer times of applied fields for uncorrelated spectra). Results are shown for a nematic LC and a nematic polymer having a similar side chain.     

'q-Titration' of long-chain and short-chain lipids differentiates between structured and mobile residues of membrane proteins studied in bicelles by solution NMR spectroscopy

'q-Titration' refers to the systematic comparison of signal intensities in solution NMR spectra of uniformly (15)N labeled membrane proteins solubilized in micelles and isotropic bicelles as a function of the molar ratios (q) of the long-chain lipids (typically DMPC) to short-chain lipids (typically DHPC). In general, as q increases, the protein resonances broaden and correspondingly have reduced intensities due to the overall slowing of protein reorientation. Since the protein backbone signals do not broaden uniformly, the differences in line widths (and intensities) enable the narrower (more intense) signals associated with mobile residues to be differentiated from the broader (less intense) signals associated with "structured" residues. For membrane proteins with between one and seven trans-membrane helices in isotropic bicelles, we have been able to find a value of q between 0.1 and 1.0 where only signals from mobile residues are observed in the spectra. The signals from the structured residues are broadened so much that they cannot be observed under standard solution NMR conditions. This q value corresponds to the ratio of DMPC:DHPC where the signals from the structured residues are "titrated out" of the spectrum. This q value is unique for each protein. In magnetically aligned bilayers (q>2.5) no signals are observed in solution NMR spectra of membrane proteins because the polypeptides are "immobilized" by their interactions with the phospholipid bilayers on the relevant NMR timescale (～10(5)Hz). No signals are observed from proteins in liposomes (only long-chain lipids) either. We show that it is feasible to obtain complementary solution NMR and solid-state NMR spectra of the same membrane protein, where signals from the mobile residues are present in the solution NMR spectra, and signals from the structured residues are present in the solid-state NMR spectra. With assigned backbone amide resonances, these data are sufficient to describe major features of the secondary structure and basic topology of the protein. Even in the absence of assignments, this information can be used to help establish optimal experimental conditions.     

External field-induced switching in nematic elastomers: A Monte Carlo study

We present a Monte Carlo study of external field-induced switching in nematic elastomers, employing a coarse-grained shearable lattice model. In large enough systems a full-wavelength Fréedericksz effect is observed --as opposed to the half-wavelength effect seen in ordinary nematics-- that clearly reflects in simulated polarized light textures, as well as in deuterium magnetic resonance spectra. The reorientation of mesogenic units is accompanied by pronounced shear deformations.     

Atomic reorientation rates in liquid chalcogenide glasses: NMR in Se and As2Se3

Temperature dependence of the NMR spectrum in liquid Se indicates that atomic reorientation in this molten ring-chain structure glass is governed by a distribution of correlation times with a median of τ^∗ = 5 × 10⁻⁵sec at 220°C. In liquid layer structure glasses at equivalent viscosity, atomic reorientation rates are not sufficient to narrow observed NMR spectra. SeSe and AsSe bonds in glassy Se and As₂Se₃ are distinguishable on the basis of their chemically shifted Se⁷⁷ NMR spectra.     

Definitive Carbon-13 Chemical Shift Assignments in 2-Substituted Adamantane Derivatives by Deuterium Isotope Effects

Deuterium isotope effects on carbon-13 chemical shifts in 5-[²H]-isotopomeres of ten 2-substituted adamantane derivatives were determined and used for complete assignment of their carbon-13 NMR spectra.

The carbon-13 NMR spectra of ten 2-substituted adamantane derivatives have been assignated by consideration of deuterium isotope effects. Some four- and five-bond downfield deuterium effects on certain chemical shifts have been measured and attributed to remote hyperconjugative interactions.     

A 2H and 14N NMR study of molecular motion in polycrystalline choline salts

²H and ¹⁴N solid-state NMR spectra of polycrystalline choline chloride, bromide, and iodide indicate that 180° cation flipping motion occurs in all three salts. From the temperature dependence of these spectra, the activation energy for this motion is determined to be 5.8 ± I kcal/mol in the iodide salt and 11 ± 1.5 kcal/mol in the chloride salt. In the bromide salt the reorientation rate is too rapid to be determined from the NMR lineshape, but the temperature dependence of the ²H quadrupole coupling parameters is indicative of a second-order phase transition at approximately 273 K. The spectral distortions in the ¹⁴N NMR spectra of the chloride and iodide salts are adequately explained using the motional model derived from the ²H NMR results, while the ¹⁴N spectra of the bromide salt show no motional effects. The axis of reorientation which is inferred from these data appears to be consistent with that indicated in a previous X-ray crystallographic study.     

Analysis of porosity in porous silicon using hyperpolarized 129Xe two-dimensional exchange experiments

The porosity in porous silicon was characterized using hyperpolarized (HP) xenon as a probe. HP xenon under conditions of continuous flow allows for the rapid acquisition of xenon NMR spectra that can be used to characterize a variety of materials. Two-dimensional exchange spectroscopy (EXSY) (129)Xe NMR experiments using HP xenon were performed to obtain exchange pathways and rates of xenon mobility between pores of different dimensions within the structure of porous silicon and to the gas phase above the sample. Pore sizes are estimated from chemical shift information and a model for pore geometry is presented.     

Effect of shear on the symmetric diblock copolymer/nanorod mixture: A dissipative particle dynamics study

The phase behaviours of a lamellar diblock copolymer/nanorod composite under steady shear are investigated using dissipative particle dynamics.We consider a wide range of nanorod concentrations,where the nanorods each have a preferential affinity to one of the blocks.Our results suggest that shear not only aligns the orientations of the diblock copolymer templates and nanorods towards flow direction,but also regulates the distribution of the nanorods within the polymer matrix.Meanwhile,the shear-induced reorientation and morphology transitions of the systems also significantly depend on the nanorod concentration.At certain nanorod concentrations,the competitions between shearinduced polymer thinning and nanorods dispersion behaviours determine the phase behaviours of the composites.For high nanorod concentrations,no morphology transition is observed,but reorientation is present,in which the sheared nanorods are arranged into hexagonal packing arrays.Additionally,the orientation behaviour of nanorods is determined directly by the applied shear,also interfered with by the shear-stretched copolymer molecules.     

分时制质子锁场系统

本文介绍了一种简便的质子锁场系统,可用于没有氟锁的电磁铁NMR谱仪做低频(如氘谱)核磁共振实验。     

Direct Determination of Motional Correlation Times by 1D MAS and 2D Exchange NMR Techniques

One- and two-dimensional static and magic-angle spinning (MAS) exchange NMR experiments for quantifying slow (τ_c> 1 ms) molecular reorientation dynamics are analyzed, emphasizing the extent to which motional correlation times can be extracteddirectlyfrom the experimental data. The static two-dimensional (2D) exchange NMR experiment provides geometric information, as well as exchange time scales via straightforward and model-free application of Legendre-type orientational autocorrelation functions, particularly for axially symmetric interaction tensors, as often encountered in solid-state²H and¹³C NMR. Under conditions of MAS, increased sensitivity yields higher signal-to-noise spectra, with concomitant improvement in the precision and speed of correlation time measurements, although at the expense of reduced angular (geometric) resolution. For random jump motions, one-dimensional (1D)exchange-inducedsidebands (EIS)¹³C NMR and the recently developed ODESSA and time-reverse ODESSA experiments complement the static and MAS two-dimensional exchange NMR experiments by providing faster means of obtaining motional correlation times. For each of these experiments, the correlation time of a dynamic process may be obtained from a simple exponential fit to the integrated peak intensities measured as a function of mixing time. This is demonstrated on polycrystalline dimethylsulfone, where the reorientation rates from EIS, ODESSA, time-reverse ODESSA, and 2D exchange are shown to be equivalent and consistent with literature values. In the analysis, the advantages and limitations of the different methods are compared and discussed.     

Theory of zero-field NMR spectra. Effects of motion

Zero-field NMR spectra of tunnelling methyl group, classically reorienting methyl group and of a pair of spins 1/2 jumping between two perpendicular orientations are calculated. A formula for the second moment of a rigid lattice is derived from a formal analogy between zero-field and high-field spectra. Fast reorientation about a perpendicular axis reduces the intramolecular second moment to 1/4 of its rigid value. The zerofield method seems to be a promising tool for the determination of tunnelling splitting or of jumping rates.     

Calculation of zero-field NMR spectra of the ammonium ion undergoing tunneling motion and fast random reorientation

Zero-field NMR spectra of the ammonium ion in the case of tunneling, tunneling and fast reorientation by 180° jumps around theC ₂ axis, tunneling and fast reorientation by 120° jumps aroundC ₃ axis are calculated.     

结晶型PEO8∶NaPF6聚电解质中晶区链段的运动

利用固体NMR 研究了高度结晶的聚氧乙烯(PEO)/六氟磷酸钠(NaPF6)（按照氧钠摩尔比8∶1 描述为PEO8∶NaPF6,分子量Mw = 1 000 和6 000 g/mol）固体聚电解质晶区链段的结构和运动．对于纯PEO 来说,晶区链段的构象交换或大角度再取向促使其¹³C 粉末线形从低温的非轴对称(δ₃₃ <δ₂₂ <δ₁₁)变成高温的轴对称线形(δ₁₁ =δ₂₂ >δ₃₃)．通过变温的¹³C 粉末线形和243 K 下的二维交换谱,PEO8∶NaPF6 晶区链段同样存在大角度再取向,且开启温度也很低(~243 K)与PEO 接近．这种长程的运动使得PEO8∶NaPF6 从低温的类轴对称(δ₃₃ <δ₂₂ <δ₁₁)变成高温的轴对称线形(δ₃₃ >δ₂₂ =δ₁₁),高温线形是PEO 高温线形的翻转．与其它PEO/Na(Li)固体聚电解质不同,PEO8∶NaPF6 中晶区链段与Na+络合后仍具有很高的运动性（与纯PEO 链段的运动性相当）,这种高分子链段和Na+协同运动促使Na+沿PEO 分子链轴向迁移,提高电导率．     

High-pressure,high-resolution NMR probe working at 400 MHZ

Abstract

A probe for obtaining high-resolution multinuclear NMR spectra at elevated pressures with a Bruker AM-400 spectrometer is described. The probe is designed for pressures up to 200 MPa and has been used between -40 to 150°C. We obtain routinely a resolution of about 1 Hz for proton (400 MHz) spectra using deuterium as an internal field lock. This probe is easily interchangeable with a commercial probe. We also describe a simple sample tube made of a 5 mm commercial NMR tube and a machinable glass cap with a total volume of about 1 cm³.     

Depolarized light scattering studies of the orientational motion in liquids of nonrigid molecules

We report depolarized Rayleigh spectra, HV, of diphenyl ether (DPE) and 1,3 diphenyl-1,3 tetramethyldisiloxane (PMS) in the temperature range of 276 to 353 K using Fabry-Perot interferometry. We have associated the single Lorentzian HV spectra with molecular reorientation in DPE and intramolecular rotation in flexible PMS under slipping boundary conditions.     

Determination of structural and dynamic characteristics of biodegradable polymers by the NMR relaxation method

A theory of the NMR spectra of heterogeneous polymer systems is proposed that makes it possible to simulate signals observed over a wide temperature range with account of spectral diffusion. Based on this theory, a technique of rapid analysis of molecular structure parameters, including the degree of crystallinity and NMR line shape, is developed. The degree of crystallinity is demonstrated to be a linear function of the area under the NMR spectrum. It is shown that this dependence, universal for a given substance, makes it possible to reliably determine the degree of crystallinity over a wide temperature range (or the fraction of low-molecular additives in composites). The NMR spectra of chitosan is simulated and compared to experimental data. The universal dependence of the degree of crystallinity on the area under the spectrum of chitosan is calculated. A comparison with experimental signals allowed determining the degree of crystallinity.     

Investigation of the surface of poly(ethylene terephthalate) films modified by vacuum ultraviolet irradiation in air

This paper reports on the results of measuring the changes in the characteristics of the surface of poly(ethylene terephthalate) films upon radiation-induced oxidation of the polymer under vacuum ultraviolet irradiation in an oxygen-containing medium. The films were irradiated by light from a sealed-off deuterium lamp with the maximum photon energy within the band (10 ±1 eV) in air under conditions where thermal destruction of poly(ethylene terephthalate) could be ignored. The functional relationship between the decrease in the film thickness and the growth of surface irregularities in the course of photoetching was established from measurements of the optical transmission spectra T (γ) of the films and investigations of the surface microrelief by atomic-force microscopy. The hydrophilic properties of the surface of the sample regions irradiated with different doses were examined by measuring the contact angle.     

Chemical shift referencing in MAS solid state NMR

Solid state 13C magic angle spinning (MAS) NMR spectra are typically referenced externally using a probe which does not incorporate a field frequency lock. Solution NMR shifts on the other hand are more often determined with respect to an internal reference and using a deuterium based field frequency lock. Further differences arise in solution NMR of proteins and nucleic acids where both 13C and 1H shifts are referenced by recording the frequency of the 1H resonance of DSS (sodium salt of 2,2-dimethyl-2-silapentane-5-sulphonic acid) instead of TMS (tetramethylsilane). In this note we investigate the difficulties in relating shifts measured relative to TMS and DSS by these various approaches in solution and solids NMR, and calibrate adamantane as an external 13C standard for solids NMR. We find that external chemical shift referencing of magic angle spinning spectra is typically quite reproducible and accurate, with better than +/-0.03 ppm accuracy being straight forward to achieve. Solid state and liquid phase NMR shifts obtained by magic angle spinning with external referencing agree with those measured using typical solution NMR hardware with the sample tube aligned with the applied field as long as magnetic susceptibility corrections and solvent shifts are taken into account. The DSS and TMS reference scales for 13C and 1H are related accurately using MAS NMR. Large solvent shifts for the 13C resonance in TMS in either deuterochloroform or methanol are observed, being +0.71 ppm and -0.74 ppm from external TMS, respectively. The ratio of the 13C resonance frequencies for the two carbons in solid adamantane to the 1H resonance of TMS is reported.     

Influence of Rayleigh-Taylor Instability on Liquid Propellant Reorientation in a Low-Gravity Environment

A computational simulation is conducted to investigate the influence of Rayleigh-Taylor instability on liquid propellant reorientation flow dynamics for the tank of CZ-3A launch vehicle series fuel tanks in a low-gravity environment. The volume-of-fluid （VOF） method is used to simulate the free surface flow of gas-liquid. The process of the liquid propellant reorientation started from initially flat and curved interfaces are numerically studied. These two different initial conditions of the gas-liquid interface result in two modes of liquid flow. It is found that the Rayleigh Taylor instability can be reduced evidently at the initial gas-liquid interface with a high curve during the process of liquid reorientation in a low-gravity environment.