Structural transitions of solvent-free oligomer-grafted nanoparticles

Novel structural transitions of solvent-free oligomer-grafted nanoparticles are investigated by using molecular dynamics simulations of a coarse-grained bead-spring model. Variations in core size and grafting density lead to self-assembly of the nanoparticles into a variety of distinct structures. At the boundaries between different structures, the nanoparticle systems undergo thermoreversible transitions. This structural behavior, which has not been previously reported, deviates significantly from that of simple liquids. The reversible nature of these transitions in solvent-free conditions offers new ways to control self-assembly of nanoparticles at experimentally accessible conditions.     

TiO2(110)-(1 × 1) supported Cu particles: An FT-RAIRS investigation

The morphology of TiO₂(110)-(1 × 1) supported Cu particles has been investigated by Fourier Transform Reflection Absorption Infrared Spectroscopy (FT-RAIRS), employing adsorbed CO as a probe molecule sensitive to local surface structure. For Cu coverage (deposited at 300 K) less than 2.85 MLE nucleated Cu particles in the range 2 nm–4 nm are formed, as indicated by a final state shift in the core level Cu(2p_3/2) binding energy and by the existence of only transmission bands in the FT-RAIRS spectra for adsorbed CO. ν_S(CO) indicates that these small particles expose sites similar to those of the stepped Cu surfaces Cu(211), Cu(311), and Cu(755). At Cu coverages in the range of 6 MLE and above, corresponding to particle sizes above 4.6 nm, ν_S(CO) indicates the predominance of (110), (100) and (111) adsorption sites. Annealing the Cu layers to 650 K results in the slight growth of the particle sizes, and transformation of the CO adsorption sites corresponding to the close packed facets. The transformation of the local dielectric from that of titania to that dominated by the Cu particle is shown to take place between 3.7 and 4.2 nm, and this change is also to a smaller extent sensitive to the dispersion of the particles.     

Activation Energies Control the Macroscopic Properties of Physically Cross‐Linked Materials

Here we show the preparation of a series of water‐based physically cross‐linked polymeric materials utilizing cucurbit[8]uril (CB[8]) ternary complexes displaying a range of binding, and therefore cross‐linking, dynamics. We determined that the mechanical strength of these materials is correlated directly with a high energetic barrier for the dissociation of the CB[8] ternary complex cross‐links, whereas facile and rapid self‐healing requires a low energetic barrier to ternary complex association. The versatile CB[8] ternary complex has, therefore, proven to be a powerful asset for improving our understanding of challenging property–structure relationships in supramolecular systems and their associated influence on the bulk behavior of dynamically cross‐linked materials.     

Formal synthesis of Abyssomicin C

An alternative strategy towards Abyssomicin C (1) is described. The key ene-diene intermediate is synthesized via a Kishi type coupling of an E/Z mixture of triene-iodide 7 and a suitably functionalized derivative of 2,4-dimethylglutaric acid. A final in situ isomerization/intramolecular Diels-Alder cyclization resulted in the formation of the known intermediate 3 as a single isomer in high yield. Further heating of 3 using excess of iodine, afforded iodo-derivative 23, having the entire carbon skeleton of Abyssomicin D.     

Directed mutagenesis alters the stereochemistry of catalysis by isolated ketoreductase domains from the erythromycin polyketide synthase

The ketoreductase (KR) domains eryKR(1) and eryKR(2) from the erythromycin-producing polyketide synthase (PKS) reduce 3-ketoacyl-thioester intermediates with opposite stereospecificity. Modeling of eryKR(1) and eryKR(2) showed that conserved amino acids previously correlated with production of alternative alcohol configurations lie in the active site. eryKR(1) domains mutated at these positions showed an altered stereochemical outcome in reduction of (2R, S)-2-methyl-3-oxopentanoic acid N-acetylcysteamine thioester. The wild-type eryKR(1) domain exclusively gave the (2S, 3R)-3-hydroxy-2-methylpentanoic acid N-acetylcysteamine thioester, while the double mutant (F141W, P144G) gave only the (2S, 3S) isomer, a switch of the alcohol stereochemistry. Mutation of the eryKR(2) domain, in contrast, greatly increased the proportion of the wild-type (2R, 3S)-alcohol product. These data confirm the role of key residues in stereocontrol and suggest an additional way to make rational alterations in polyketide antibiotic structure.     

Numerical experiments on the efficiency of local grid refinement based on truncation error estimates

Local grid refinement aims to optimise the relationship between accuracy of the results and number of grid nodes. In the context of the finite volume method no single local refinement criterion has been globally established as optimum for the selection of the control volumes to subdivide, since it is not easy to associate the discretisation error with an easily computable quantity in each control volume. Often the grid refinement criterion is based on an estimate of the truncation error in each control volume, because the truncation error is a natural measure of the discrepancy between the algebraic finite-volume equations and the original differential equations. However, it is not a straightforward task to associate the truncation error with the optimum grid density because of the complexity of the relationship between truncation and discretisation errors. In the present work several criteria based on a truncation error estimate are tested and compared on a regularised lid-driven cavity case at various Reynolds numbers. It is shown that criteria where the truncation error is weighted by the volume of the grid cells perform better than using just the truncation error as the criterion. Also it is observed that the efficiency of local refinement increases with the Reynolds number. The truncation error is estimated by restricting the solution to a coarser grid and applying the coarse grid discrete operator. The complication that high truncation error develops at grid level interfaces is also investigated and several treatments are tested.     

Encapsulation of Crabtree's Catalyst in Sulfonated MIL‐101(Cr): Enhancement of Stability and Selectivity between Competing Reaction Pathways by the MOF Chemical Microenvironment

Crabtree's catalyst was encapsulated inside the pores of the sulfonated MIL‐101(Cr) metal–organic framework (MOF) by cation exchange. This hybrid catalyst is active for the heterogeneous hydrogenation of non‐functionalized alkenes either in solution or in the gas phase. Moreover, encapsulation inside a well‐defined hydrophilic microenvironment enhances catalyst stability and selectivity to hydrogenation over isomerization for substrates bearing ligating functionalities. Accordingly, the encapsulated catalyst significantly outperforms its homogeneous counterpart in the hydrogenation of olefinic alcohols in terms of overall conversion and selectivity, with the chemical microenvironment of the MOF host favouring one out of two competing reaction pathways.     

Novel synthesis of (−)-trans-Δ9,11-tetrahydrocannabinol

Addition of hydrogen chloride gas to a solution of Δ⁸-tetrahydrocannabinol in dry dichloromethane at -60° in the presence of zinc chloride results in the formation of a higher concentration of 9-α-chlorohexa-hydrocannabinol (75%) than the thermodynamically more stable 9-β-chlorohexahydrocannabinol (25%). The two isomers can be separated by reverse-phase hplc. Elimination of hydrogen chloride from 9-α-chlorohexa-hydrocannabinol using potassium t-amylate under anhydrous conditions gives exclusively Δ^9,11-tetrahydrocannabinol in overall yield of 65%.     

Total Synthesis of Vancomycin Aglycon—Part 3: Final Stages

A triazene-based synthetic strategy for the construction of the complex biaryl ethers and a Suzuki coupling reaction were the key steps in the synthesis of precursor 1 of the aglycon of vancomycin, which already contains the complete skeleton of the target compound. The cleavage of the triazene unit from the D ring and the removal of the other protecting groups led to the aglycon of vancomycin. These strategies should be particularly valuable for the synthesis of other naturally occurring glycopeptide antibiotics and offer opportunities for the synthesis of combinatorial libraries of compounds of the vancomycin family for chemical biology studies.     

Effect of the type of organic modifier on the polymerization kinetics and the properties of poly(methyl methacrylate)/organomodified montmorillonite nanocomposites

A series of organomodified montmorillonite clays (OMMTs) such as intercalated modified montmorillonite with alkylammonium or alkylphosphonium salts (AA-MMT or AP-MMT) and double modified MMT with alkylammonium or alkylphosphonium salts and silane coupling agent (SAA-MMT or SAP-MMT) was successfully prepared in this study. The effect of the amount of nanofiller and type of organic modifier of the OMMT on poly(methyl methacrylate) (PMMA)/OMMT nanocomposites synthesized by in situ bulk polymerization was investigated. The structural and morphological characteristics of the obtained nanocomposites were studied by means of X-ray diffraction and transmission electron microscopy, indicating that exfoliation is more likely to occur in case of nanocomposites with small amounts of AA-MMT and SAA-MMT. The kinetic study results showed that the presence of AA-MMT enhances polymerization kinetics, while AP-MMT acts rather as a reaction retarder. The presence of the nanofiller and the augmentation of the OMMT content increased the thermal stability of all nanocomposites, as measured by thermogravimetric analysis, as well as their average molecular weight measured by gel permeation chromatography. Measurements of the tensile properties revealed that the Young’s modulus increased for all nanocomposites along with a decrease of the ultimate strain, while the tensile strength varied regardless of the extent of exfoliation.