NMR relaxation time measurements of solvent effects in an organocatalysed asymmetric aldol reaction over silica SBA-15 supported proline

Immobilisation of organocatalysts onto solid supports represents a very promising solution to tackle their low productivity by enabling their reuse. Herein, the use of NMR relaxation measurements, coupled with reaction...

Double mutant of chymotrypsin inhibitor 2 stabilized through increased conformational entropy

The conformational heterogeneity of a folded protein can affect both its function but also stability and folding. We recently discovered and characterized a stabilized double mutant (L49I/I57V) of the protein CI2 and showed that state-of-the-art prediction methods could not predict the increased stability relative to the wild-type protein. Here we have examined whether changed native state dynamics, and resulting entropy changes, can explain the stability changes in the double mutant protein, as well as the two single mutant forms. We have combined NMR relaxation measurements of the ps-ns dynamics of amide groups in the backbone and the methyl groups in the side-chains with molecular dynamics simulations to quantify the native state dynamics. The NMR experiments reveal that the mutations have different effects on the conformational flexibility of CI2: A reduction in conformational dynamics (and entropy) of the native state of L49I variant correlates with its decreased stability, while increased dynamics of the I57V and L49I/I57V variants correlates with their increased stability. These findings suggest that explicitly accounting for changes in native state entropy might be needed to improve the predictions of the effect of mutations on protein stability.

Elastic, Dynamic Viscoelastic and Model-Derived Fibril-Reinforced Poroelastic Mechanical Properties of Normal and Osteoarthritic Human Femoral Condyle Cartilage

Osteoarthritis (OA) degrades articular cartilage and weakens its function. Modern fibril-reinforced poroelastic (FRPE) computational models can distinguish the mechanical properties of main cartilage constituents, namely collagen, proteoglycans, and fluid, thus, they can precisely characterize the complex mechanical behavior of the tissue. However, these properties are not known for human femoral condyle cartilage. Therefore, we aimed to characterize them from human subjects undergoing knee replacement and from deceased donors without known OA. Multi-step stress-relaxation measurements coupled with sample-specific finite element analyses were conducted to obtain the FRPE material properties. Samples were graded using OARSI scoring to determine the severity of histopathological cartilage degradation. The results suggest that alterations in the FRPE properties are not evident in the moderate stages of cartilage degradation (OARSI 2-3) as compared with normal tissue (OARSI 0-1). Drastic deterioration of the FRPE properties was observed in severely degraded cartilage (OARSI 4). We also found that the FRPE properties of femoral condyle cartilage related to the collagen network (initial fibril-network modulus) and proteoglycan matrix (non-fibrillar matrix modulus) were greater compared to tibial and patellar cartilage in OA. These findings may inform cartilage tissue-engineering efforts and help to improve the accuracy of cartilage representations in computational knee joint models.

Freeze–Thaw Effect on Road Concrete Containing Blast Furnace Slag: NMR Relaxometry Investigations

The present work investigates the effect of freeze–thaw cycles on the porosity of three mixtures of road concrete containing blast furnace slag in comparison with two mixtures made with conventional materials. The main technique used in our investigations is nuclear magnetic resonance (NMR) relaxometry. This permitted the extraction of information with respect to the freeze–thaw effect on pore-size distribution, which influences both the mechanical strength and the molecular transport through the material. Moreover, by using this technique, the structure of the air voids was analyzed for the entire pore system in the cement paste and the aggregate particles. The samples under study were first dried in a vacuum oven and then saturated with water or cyclohexane where the distribution of the transverse relaxation times of the protons was recorded. The NMR relaxation measurements were performed on samples extracted from specimens maintained at 300 freeze–thaw cycles and on control samples extracted from specimens kept in water during the freeze–thaw period. Scanning Electron Microscopy (SEM) was used to analyze the microstructure of concrete samples in order to obtain information about the pore sizes and the distance between them. The results from the NMR relaxation measurements were consistent with those obtained by using standard techniques for determining the porosity and the freeze–thaw resistances. The investigations made it possible to establish the optimal composition of blast furnace slag that can be incorporated into road concrete compositions. This non-invasive technique can also complete standard techniques for assessing the porosity and the progress of internal cracks during the freeze–thaw test.

Functional Group Resolved Nuclear Spin Relaxation in Porous Media

Understanding solid-fluid interactions within porous materials is critical for their efficient utilisation across chemical reaction and separation processes. However, detailed characterisation of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we detail here the application of low magnetic field 2D ¹H nuclear spin relaxation measurements as a non-invasive probe of sorbate/sorbent interactions, exploring the relaxation characteristics exhibited by liquid adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of such measurements to distinguish functional group-specific relaxation phenomena across a diverse range of protic adsorbates of wide importance as solvents, reagents, and hydrogen carriers, with distinct relaxation environments assigned to the alkyl and hydroxyl moieties of the confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics.

Functional Group Resolved Nuclear Spin Relaxation in Porous Media

Understanding solid-fluid interactions within porous materials is critical for their efficient utilisation across chemical reaction and separation processes. However, detailed characterisation of interfacial phenomena within such systems is hampered by their optically opaque nature. Motivated by the need to bridge this capability gap, we detail here the application of low magnetic field 2D ¹H nuclear spin relaxation measurements as a non-invasive probe of sorbate/sorbent interactions, exploring the relaxation characteristics exhibited by liquid adsorbates confined to a model mesoporous silica. For the first time, we demonstrate the capacity of such measurements to distinguish functional group-specific relaxation phenomena across a diverse range of protic adsorbates of wide importance as solvents, reagents, and hydrogen carriers, with distinct relaxation environments assigned to the alkyl and hydroxyl moieties of the confined liquids. Uniquely, this relaxation behaviour is shown to correlate with adsorbate acidity, with the observed relationship rationalised on the basis of surface-adsorbate proton exchange dynamics.