Applications of Two-Dimensional 1H NMR Methods to Photo-Chemically Induced Dynamic Nuclear Polarisation Spectroscopy

Photo-CIDNP is a useful technique to identify surface residues in proteins and to assign resonances in their ¹H NMR spectra by the spectral simplification that is obtained. In spite of this simplification, conventional photo-CIDNP spectra can be quite complex due to spectral overlap. For this reason two-dimensional (2D) methods are welcome. We present combinations of photo-CIDNP with 2D J-correlated spectroscopy (CIDNP-COSY) and with 2D NOE spectroscopy (CIDNP-NOESY). In these experiments we insert a saturation pulse sequence and a short laser-irradiation period at the beginning of the preparation period to generate CIDNP, leaving the remaining of the pulse scheme essentially unaltered. The CIDNP-COSY and CIDNP-NOESY spectra of a hen egg-white (HEW) lysozyme are presented. The CIDNP-NOESY spectrum of lysozyme is compared with the results from 1D cross-polarisation experiments on the same protein. CIDNP-NOESY spectra of lysozyme with and without inhibitor NAG are compared.     

Ultrafast 2D IR vibrational echo spectroscopy

The experimental technique and applications of ultrafast two-dimensional infrared (2D IR) vibrational echo spectroscopy are presented. Using ultrashort infrared pulses and optical heterodyne detection to provide phase information, unique information can be obtained about the dynamics, interactions, and structures of molecular systems. The form and time evolution of the 2D IR spectrum permits examination of processes that cannot be studied with linear infrared absorption experiments. Three examples are given: organic solute-solvent complex chemical exchange, dynamics of the hydrogen-bond network of water, and assigning peaks in an IR spectrum of a mixture of species.     

Numerical and experimental study on spout elevation in spout‐fluidized beds

The effect of elevating the spout on the dynamics of a spout‐fluidized bed, both numerically and experimentally is studied. The experiments were conducted in a pseudo‐two‐dimensional (2‐D) and a cylindrical three dimensional (3‐D) spout‐fluidized bed, where positron emission particle tracking (PEPT) and particle image velocimetry (PIV) were applied to the pseudo‐2‐D bed, and PEPT and electrical capacitance tomography (ECT) to the cylindrical 3‐D bed. A discrete particle model (DPM) was used to perform full 3‐D simulations of the bed dynamics. Several cases were studied, that is, beds with spout heights of 0, 2, and 4 cm. In the pseudo‐2‐D bed, the spout‐fluidization and jet‐in‐fluidized‐bed regime, were considered first, and it was shown that in the spout–fluidization regime, the expected dead zones appear in the annulus near the bottom of the bed as the spout is elevated. However, in the jet‐in‐fluidized‐bed regime, the circulation pattern of the particles is affected, without the development of stagnant zones. The jet‐in‐fluidized‐bed regime was further investigated, and additionally the experimental results obtained with PIV and PEPT were compared with the DPM simulation results. The experimental results obtained with PIV and PEPT agreed mutually very well, and in addition agreed well wtih the DPM results, although the velocities in the annulus region were slightly over predicted. The latter is probably due to the particle‐wall effects that are more dominant in pseudo‐2‐D systems compared with 3‐D systems. In the jet‐in‐fluidized‐bed regime, the background gas velocity is relatively high, producing bubbles in the annulus that interact with the spout channel. In the case of a non elevated spout, this interaction occurs near the bottom of the bed. As the spout is elevated, this interaction is shifted upwards in the bed, which allows the bubbles to remain undisturbed providing the motion of the particles in the annulus near the bottom of the bed. As a result, no dead zones are created and additionally, circulation patterns are vertically stretched. These findings were also obtained for the cylindrical 3‐D bed; although, the effects were less pronounced. In the cylindrical 3‐D bed the PEPT results show that the effect on the bed dynamics starts at h_spout =1 4 cm, which is confirmed by the ECT results. Additionally, ECT measurements were conducted for h_spout =1 6 cm to verify if indeed the effect happens at larger spout heights. The root mean square of the particle volume fraction slightly increased at h_spout =1 2 cm, whereas a larger increase is found at h_spout = 4 and 6 cm, showing that indeed more bubbles are formed. The presented results have not been reported so far and form valuable input information for improving industrial granulators. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2524–2535, 2012     

Femtosecond Laser Spectroscopy and Computer Simulations of Barrierless Isomerization in Solution

The barrierless isomerization of 1,1-diethyl-4,4-cyanine in alcohol solutions has been studied with 75-fs laser pulses in transient absorption experiments. The measured dynamics are compared with Monte-Carlo simulations based on the BFO-theory (Bagchi, B.; Fleming, G.R.; Oxtoby, D.W.J. Chem. Phys. 1983. 78: 7375) for condensed-phase barrierless isomerizations, and the viscosity dependence of the long-time exponential decay is well reproduced with a coherent set of parameters. In the most viscous solvents, early-time (≲ 1 ps) kinetics are observed which are characteristic of damped wavepacket dynamics in the reaction coordinate.     

Two-Dimensional Deuterium NMR Exchange Spectroscopy in Liquid Crystalline Solutions

A theoretical analysis is given of deuterium 2D exchange spectroscopy using Zeeman- and quadrupole-order experiments in liquid crystalline solutions. For the analysis, a phenomenological vector model for spin I = 1 nuclei under the effect of the quadrupole Hamiltonian and rf pulses is employed, which makes it easy to follow the evolution of the various coherences during the pulse sequences. In both experiments several types of cross-peaks are obtained; however, only part of them are relevant to the exchange process. It is shown that proper combination of the signals from the Zeeman- and quadrupole-order experiments can lead to 2D exchange spectra with “pure” exchange cross-peaks as the only off-diagonal signals. These exchange cross-peaks can provide estimates for the exchange rates and indicate the relative signs of the quadrupole interactions in the exchanging sites. The method is applied to two compounds which undergo ring inversion, i.e., cyclohex- ane-d₁₂ and 1,4-dioxane-d₈, dissolved in liquid crystalline solvents. In the Appendices procedures for phase cycling are discussed, and peak intensities for a general two-site 2D exchange spectrum are derived.     

Molecular Weight Polydispersity Effects on Diffusion at Polymer/Polymer Interfaces

The effect of molecular weight distribution (MWD) on diffusion at symmetric polymer/polymer interfaces is investigated by rheological tools. A new model allowing the determination of a self‐diffusion coefficient of polydisperse polymer systems is presented. The model is based on the double reptation theory and Doi and Edwards' molecular dynamics applied to A/A polymers brought into intimate contact in the molten state. The material parameters for the model are obtained from linear oscillatory shear experiments, in which the dynamic shear modulus is measured in parallel plate geometry under a small amplitude of deformation as a function of time and frequency for a sandwich‐like assembly. The experiments were conducted on polystyrene (PS) blends with constant weight average molecular weight (M_w) but with variable number average molecular weights (M_n). The measured self‐diffusion coefficients showed that the presence of short molecules in the blend increases the mean value of the self‐diffusion coefficient and the magnitude of such increase can be quantitatively evaluated by the proposed model.     

1H-Observe 1H?2H Dipolar Recoupling by REDOR and Rotary Resonance Recoupling

The measurement of heteronuclear dipolar couplings by solid-state NMR is an important tool for determining structures in solids. ¹H-observe ¹H ²H REDOR and rotary resonance recoupling experiments with fast magic-angle spinning are presented. These dipolar recoupling experiments show promise for measuring heteronuclear dipolar couplings with ¹H nuclei. Potential limitations of the experiments include short transverse relaxation times of the ¹H magnetization and Bloch Siegert effects.     

On reduced modeling of mass transport in wavy falling films

In many industrial units such as packing columns, falling film reactors, etc., the liquid phase is designed as a falling film. It is well known that the mass and heat transfer in laminar wavy film flows is significantly enhanced compared to flat films. The kinetic phenomena underlying the increase in mass and heat transfer are, however, still not fully understood. For an efficient design of falling film units, computational models that account for these enhanced transport mechanisms are of key importance. In this article, we present a reduced modeling approach based on a long‐wave approximation to the fluid dynamics of the film. Furthermore, we introduce a new two‐dimensional (2D) high‐resolution laser‐induced luminescence measurement technique. Both in the numerical simulation results and in the high‐resolution 2D‐concentration measurements obtained in the experiments we observe similar patterns of high concentrations locally, especially in the areas close to the wave hump. © 2018 American Institute of Chemical Engineers AIChE J, 64: 2265–2276, 2018     

Unraveling the Interaction between the LPS O‐Antigen of Burkholderia anthina and the 5D8 Monoclonal Antibody by Using a Multidisciplinary Chemical Approach,with Synthesis,NMR, and Molecular Modeling Methods

The interaction between the O‐chain from the lipopolysaccharide from Burkholderia anthina and a lipopolysaccharide‐specific monoclonal antibody (5D8) has been studied at high resolution by NMR spectroscopy. In particular, the 5D8‐bound epitope of the saccharide entity has been unraveled by a combination of saturation transfer difference (STD) and transferred NOESY (tr‐NOESY) experiments performed on the 5D8/polysaccharide complex. To dissect the fine details of the molecular recognition events, further experiments with simpler carbohydrate ligands were carried out. Thus, experiments were also performed with ad hoc synthesized trisaccharide and hexasaccharide O‐antigen repeating units. By using this multidisciplinary approach (chemical synthesis, NMR spectroscopy and molecular dynamics simulation), determination of the binding epitope and the contribution to the binding of the sugar units composing the O‐chain have been determined.     

Modeling of the Low-Frequency Noise in Thermal Lens Spectrometry

The low-frequency noise observed in thermal lens spectrometry (TLS) can be modeled by assuming that the heated region, constituted by the thermal lens gradient and associated convective stream, behaves as a weakly damped harmonic oscillator with a natural frequency, v_o, which is forced to move at an externally imposed pump frequency, v_p. Out-of-phase lower-frequency oscillations of the TLS signal can be produced both by transient events, such as the beginning of the TLS experiment and small changes in the pump beam stability, and by drift of boundary conditions, such as the temperature of the surroundings. A model is developed and checked using 1-(2-pyridylazo)-2-napthol (PAN) solutions in silicone oil. Consequences of analytical interest are drawn; e.g., the signal-to-noise ratio of the TLS experiments is improved by pumping at the resonance frequency, where v_p = v_o.