High-Resolution 1H Solid-State NMR Spectroscopy Using Windowed LG4 Homonuclear Dipolar Decoupling

We investigate the optimal implementation of windowed LG4 decoupling for the direct acquisition of high-resolution ¹H solid-state NMR spectra in the moderate magic-angle spinning regime (ω_r<2π × 35 kHz). We determine how the optimal value of the azimuth of the LG rotation axis, α, is affected by the choice of windowing parameters. We find that for both the windowless and windowed implementation of LG4, the optimal value of α is that for which the chemical-shift scaling factor is approximately 0.43. We then provide an analytical expression for estimating the chemical-shift scaling factor as a function of both α and the windowed decoupling parameters, which allows the optimal value of α to be easily determined for any implementation of LG4. We also introduce a simple and general method for improving the performance of any phase-modulated homonuclear dipolar decoupling sequence by compensating for pulse imperfection errors that accumulate in windowed spectra due to the repeated switching of the RF irradiation. This method involves the introduction of short (<0.5 µs) compensation pulses at the start and end of each decoupling pulse, the duration and phase of which are chosen to cancel the effects of the amplitude and phase transients that arise as a result of the RF switching. We demonstrate how this method can be implemented for homonuclear dipolar decoupling sequences such as wPMLG and wLG4 to reduce the chemical-shift scaling factor distortions generated by phase transients such that high-quality, high-resolution ¹H NMR spectra can be acquired at arbitrary RF offsets.     

Homonuclear Decoupling of 1H Dipolar Interactions in Solids by means of Heteronuclear Recoupling

Line narrowing has been traditionally achieved in solid-state ¹H NMR spectroscopy by applying pulse sequences that combine multiple-pulse operations with magic-angle spinning (MAS), to effectively average out the dipole dipole homonuclear Hamiltonian. The present study explores a new alternative that departs from the usual concept of directly acting on the strongly coupled spins with radiofrequency pulses; instead, we seek to achieve a net homonuclear dipolar decoupling in solids by exploring the reintroduction of MAS-averaged heteronuclear dipolar couplings between the ¹H nuclei and directly bonded ¹³C or ¹⁵N nuclei. This recoupling anti-recoupling (RaR) scheme thus relies on the recoupling of the dipolar interaction with heteronuclear spins, which, under fast MAS, will exceed the strength and will not commute with the homonuclear ¹H ¹H coupling one is intending to average out. Subsequent removal (“antiRecoupling”) of these heteronuclear interactions can lead to narrowed ¹H resonances, without ever pulsing on the aforementioned channel. The line-narrowing properties of RaR are illustrated with numerical simulations and with experiments on model organic solids.     

去耦室压力变化对脉动燃烧器尾管传热的影响

去耦室是脉动燃烧器的重要部件,除降低燃烧噪声外,其另一作用是保证尾管出口声学边界条件,维持整个燃烧器的运行性能。在一台无阀自激脉动燃烧器尾部建立了去耦室压力控制系统,通过调节引风机前的阀门开度来改变去耦室内部压力即尾管出口压力大小（调节范围-10～10 kPa）,实验研究了去耦室压力变化对脉动燃烧器尾管传热的影响。结果表明：当去耦室压力高于或低于大气压力时,尾管中的传热系数均能提高,而去耦室压力为负值时,尾管传热系数相对较高;燃烧室压力幅值的大小和速度比的大小均能反映传热系数的高低。     

Selective multi-component diffusion measurement in zeolites by pulsed field gradient NMR

The potential of pulsed field gradient (PFG) NMR for selective diffusion measurement in multi-component liquids is far from being fulfilled in multi-component diffusion studies with zeolites. We present two recent developments in PFG NMR instrumentation, which will significantly improve the measuring conditions for multi-component diffusion in zeolites and other nanoporous materials. They include options for an enhancement of the sensitivity with respect to smaller displacements by a novel principle of field gradient pulse matching and with respect to selectivity between different components by combining PFG NMR with magic angle spinning (MAS) NMR with a microimaging gradient system. The potentials and limitations of the two options are demonstrated by the first results of selective PFG NMR self-diffusion measurements with zeolitic adsorbate–adsorbent systems containing as much as four different species of guest molecules.     

一种纤维生产线水浴牵伸过程的智能协同解耦控制

提出了一种智能协同解耦控制器,用于纤维生产线中的水浴牵伸槽的液位-浓度复合控制。该控制器由一个控制中枢、多个控制解耦单元及相应的输出单元组成。控制中枢统一协调各控制解耦单元,多个控制解耦单元独立作用并互相交换信息进行对象解耦,控制信号经输出单元综合后作用于控制对象。仿真结果表明,该智能协同解耦控制器能够快速响应控制量的变化,实现耦合控制量的完全解耦和无超调平滑调节,对于纤维生产的牵伸过程较传统控制方法具有更好的控制性能。     

Molecular Alignment Induced by Ultrashort Laser Pulses and Its Impact on Molecular Motion

Spectroscopy aims at extracting information about matter through its interaction with light. However, when performed on gas and liquid phases as well as solid phases lacking long-range order, the extracted spectroscopic features are in fact averaged over the molecular isotropic angular distributions. The reason is that light–matter processes depend on the angle between the transitional molecular dipole and the polarization of the light interacting with it. This understanding gave birth to the constantly expanding field of “laser-induced molecular alignment”. In this paper, we attempt to guide the readers through our involvement (both experimental and theoretical) in this field in the last few years. We start with the basic phenomenon of molecular alignment induced by a single pulse, continue with selective alignment of close molecular species and unidirectional molecular rotation induced by two time-delayed pulses, and lead up to novel schemes for manipulating the spatial distributions of molecular samples through rotationally controlled scattering off inhomogeneous fields and surfaces.     

DECOUPLER DESIGN AND CONTROL SYSTEM TUNING BY INA FOR DISTILLATION COMPOSITION CONTROL†

Six distillation column models have been used in studies of the usefulness of the Inverse Nyquist Array (INA) method for design of dual composition control for distillation. Five of the column models are experimental, one describing an industrial column, the others four pilot plants. One column model is obtained by modeling from first principles.

The control strategies investigated and compared are multiloop SISO, 2-way decoupling and l-way decoupling. The control variables are the standard ones, i.e. reflux flow and boilup.

In most of the cases INA has been found to be a useful tool for design of the loops and for comparison of the different control approaches. INA has also been found to be useful for simultaneous tuning of the decouplers and the feedback controllers.

For 2-way decoupling the criterion to minimize interaction at the critical frequency for each primary feedback loop has been found useful in most, but not all, cases. The scheme can be designed by pure gains in the decouplers and there is no reason to introduce dynamics into the decouplers—the systems studied are already sufficiently rich in dynamics.

INA has been found to be a suitable vehicle for the choice between the two possible l-way decoupling schemes.

With the design approach taken, l-way decoupling has been found to provide considerably better control quality than 2-way decoupling in two of the six systems, the differences in control quality being small in the other cases.

The effect of model mismatching on the results, caused e.g. by process nonlinearities, is discussed and simple rules to decrease the parameter sensitivity for 2-way decoupling schemes are given. When model mismatching is considered, the advantage of l-way decoupling over 2-way decoupling seems to increase.

One deficiency of the INA design as used in this paper is that it does not single out the design which is to be preferred on the grounds of robustness.     

Detection of free chloride in concrete by NMR

Laboratory experiments to detect chloride in a cement matrix using pulse nuclear magnetic resonance (NMR) were conducted. The coils were in the centimeter scale and the magnetic field was 2.35 T. NMR signals were obtained from both aqueous chloride solution and samples of both regular and white Portland cement (WPC). A concrete sample from a sidewalk that had been in the field for 20 years was also tested. The experiments demonstrated that the signal-to-noise ratio (SNR) for a centimeter-scale cement sample volume is so small, even after averaging, that sample volumes much lower than that are unlikely to produce measurable signals at fields of 1 T or below. The consequence is that the potential for realizing an embedded NMR-based sensor including the magnet is low. Parametric studies identify feasible alternative coil diameters and magnetic field strengths for detecting chloride ion concentrations in hardened concrete.     

Seed oil determination without weighing and drying the seeds by combined free induction decay and spin-echo nuclear magnetic resonance signals

The free induction decay (FID) and echo signals in a spin-echo pulse sequence have been used for seed oil determination without weighing and drying the seeds with nuclear magnetic resonance (NMR) equipment that has a magnetic field of low homogeneity. Earlier known methods, based on use of the FID signal to determine seed oil, become inapplicable when the magnetic field homogeneity is poor, because the angular position of seed significantly affects the signal. The present method, which elegantly eliminates the angular dependence, involves sampling the FID signal at 10 μs after a 90° pulse and the subsequent echo signal at 100 μs formed by applying a 180° pulse at 50 μs. Such short pulse spacing in spin-echo sequence produces almost a full oil signal. It also eliminates the effects of sample-to-sample variation inT ₂ and molecular diffusion on oil signal. The oil values obtained by this method are in good agreement (correlation for mustard: 0.952; linseed: 0.99; and for peanut: 0.912) with the values obtained by the well established and accurate pulsed NMR method, which is based on the measurement of the FID signal of oil in dried and weighed seeds.     

Pumped double quantum dot with spin-orbit coupling

We study driven by an external electric field quantum orbital and spin dynamics of electron in a one-dimensional double quantum dot with spin-orbit coupling. Two types of external perturbation are considered: a periodic field at the Zeeman frequency and a single half-period pulse. Spin-orbit coupling leads to a nontrivial evolution in the spin and orbital channels and to a strongly spin- dependent probability density distribution. Both the interdot tunneling and the driven motion contribute into the spin evolution. These results can be important for the design of the spin manipulation schemes in semiconductor nanostructures.     

NMR study of intrinsic diffusion and reaction in CsNaX type zeolites

In this contribution the catalytic behaviour of the zeolites CsNaX-60 and CsNaX-60·8CsOH (impregnated with eight CsOH per unit cell) was studied. As a model reaction, the conversion of isopropanol to acetone as the product of basic catalysis or to propene as the product of acid catalysis was chosen. The intracrystalline self-diffusivities of isopropanol, acetone and propene in these zeolites and in NaX were measured with the pulsed field gradient (PFG) NMR technique. Self-diffusivity measurements of propane and water were performed to characterize these three zeolites. ¹³C MAS NMR studies with proton decoupling were used to test the cesium containing zeolites for acid or basic catalytic activity.     

民用解耦燃煤炉中的NO x 和CO同时减排

典型民用解耦燃煤炉具有底部连通的两个分别被称为热解室和燃烧室的并列炉膛，煤炭从热解室上部加入，空气通过热解室底部的倾斜炉排引入。结合煤炭燃烧过程中的氮转移路线与解耦炉中的气体循环流动特征，定性分析了民用解耦燃煤炉中的NO _x 和CO同时减排机理，并在此基础上对配风和煤种等因素对NO和CO排放的影响进行了定量实验研究。结果表明，民用解耦燃煤炉特有的结构特征和通风方式有利于NO _x 和CO的同时减排，解耦炉具与洁净型煤匹配可显著降低综合污染物排放。     

Homonuclear Magnetization Transfer Experiments Using Isotropic and Nonisotropic Mixing Schemes

The principles of homonuclear magnetization transfer via isotropic and non-isotropic mixing schemes are discussed. Practical aspects of such experiments concern the minimization of the generation of multiple quantum coherence, minimization of rf power requirements, suppression of NOEs during mixing and minimization of relaxation losses. The analogy between these experiments and heteronuclear decoupling is briefly discussed. The efficiencies of several mixing schemes are compared and it is demonstrated experimentally that the resolution and sensitivity of the homonuclear cross polarization methods can be superior to the conventional COSY experiment.     

核磁共振测井仪发射电路研究

设计了一种用于核磁共振测井仪的脉冲发射电路。利用AD5930产生脉冲数、持续时间和间隔时间可控的周期脉冲序列。采用场效应管H桥电路及专用的驱动芯片,提高了场效应管的开关速度,减小了激励脉冲电压的上升时间。实验表明:电路产生的脉冲幅度高、宽度窄,能有效地激励共振线圈探头,可以满足核磁共振测井的要求。     

PFG NMR investigation of hydrocarbon diffusion in large NaX zeolite crystals: Effect of internal field gradients on diffusion data

Self-diffusion coefficients for intracrystalline diffusion of hydrocarbon molecules adsorbed in large crystals of NaX zeolite have been measured by the pulsed field gradient (PFG) NMR technique, at ambient temperature and at different diffusion times (from 6 to 12 ms). Two NMR pulse sequences, stimulated and 13-interval bipolar spin echo, were used to examine the influence of internal field gradients on diffusion data. For both sequences the effective self-diffusion coefficient of the guest molecules was found to decrease with increasing observation times. The extrapolated intracrystalline diffusion coefficient is independent of the NMR sequence. In contrast, the estimated extent of molecular diffusion depends strongly on the pulse program. For the small molecules (butane to hexane), the domain size, R, of restricted diffusion obtained with the stimulated spin-echo sequence is smaller than the crystal dimension whereas R is always comparable to it when the 13-interval pulse sequence is used. This shows the effect of internal field gradients on the diffusion data leading to wrong values of R if the stimulated pulse sequence is used. The light hydrocarbons diffuse freely inside the zeolite particles whereas the crystal boundaries act as reflecting surfaces, as previously observed. On the other hand, even with the 13-interval pulse sequence, the smaller values of R obtained for large molecules as n-heptane and octane shows that their displacement is hindered by restrictions in the NaX macro-crystals.     

Towards a protocol for solution structure determination of copper(II) proteins: the case of Cu(II)Zn(II) superoxide dismutase

We have developed an optimized protocol to solve the solution structure of copper(II) proteins. After assignment, proton-proton NOEs are used for the shell where 1H spectra are conveniently observed. In a shell closer to the metal ion, 13C NMR spectra with band-selective homonuclear decoupling provide the assignment of all nuclei except for those of the metal ligands. A convenient method for the measurement of 13C longitudinal-relaxation rates (R1) of carbonyls and carboxylate moieties is proposed. 1H NOEs and 1H and 13C R1 data are sufficient to produce a good/reasonable solution structure, as demonstrated for a monomeric species of superoxide dismutase, a 153-residue protein.     

wPMLG-5 Spectroscopy of Self-Aggregated BChl e in Natural Chlorosomes of Chlorobaculum Limnaeum

¹H magic angle spinning (MAS) nuclear magnetic resonance (NMR), employing rapid spinning and the wPMLG-5 pulse sequence, was used to explore the possibility for performing ¹H solid state NMR of a light-harvesting organelle, the chlorosome antenna of Chlorobaculum limnaeum. This natural antenna system is built from bacteriochlorophyll e (BChl e) molecules that are self-assembled to form a supramolecular scaffold for in vivo harvesting of light. We present preliminary data on this chlorosome species and address the feasibility of performing wPMLG spectroscopy, in terms of high power irradiation on a fragile biological sample. In parallel, enhancing the ¹H shift dispersion from the magnetic field can help to resolve signals from protons that resonate downfield. Different line narrowing mechanisms operating in parallel provide access to resolving selected ¹H signals collected from the moderately sized and chemically diverse BChl e molecular motif in the chlorosome scaffold. These discoveries will be helpful for future studies of structural and functional characteristics of self-assembled natural and artificial light-harvesting molecules.     

A RELATIONSHIP BETWEEN CHEMICAL STRUCTURE AND THE CRITICAL TEMPERATURE

Six distillation column models have been used in studies of the usefulness of the Inverse Nyquist Array (INA) method for design of dual composition control for distillation. Five of the column models are experimental, one describing an industrial column, the others four pilot plants. One column model is obtained by modeling from first principles.

The control strategies investigated and compared are multiloop SISO, 2-way decoupling and l-way decoupling. The control variables are the standard ones, i.e. reflux flow and boilup.

In most of the cases INA has been found to be a useful tool for design of the loops and for comparison of the different control approaches. INA has also been found to be useful for simultaneous tuning of the decouplers and the feedback controllers.

For 2-way decoupling the criterion to minimize interaction at the critical frequency for each primary feedback loop has been found useful in most, but not all, cases. The scheme can be designed by pure gains in the decouplers and there is no reason to introduce dynamics into the decouplers—the systems studied are already sufficiently rich in dynamics.

INA has been found to be a suitable vehicle for the choice between the two possible l-way decoupling schemes.

With the design approach taken, l-way decoupling has been found to provide considerably better control quality than 2-way decoupling in two of the six systems, the differences in control quality being small in the other cases.

The effect of model mismatching on the results, caused e.g. by process nonlinearities, is discussed and simple rules to decrease the parameter sensitivity for 2-way decoupling schemes are given. When model mismatching is considered, the advantage of l-way decoupling over 2-way decoupling seems to increase.

One deficiency of the INA design as used in this paper is that it does not single out the design which is to be preferred on the grounds of robustness.