Monitoring the Transition from Spherical to Polymer‐like Surfactant Micelles Using Small‐Angle X‐Ray Scattering

Despite over a century of modern surfactant science, the kinetic pathways of morphological transitions in micellar systems are still not well understood. This is mainly as a result of the lack of sufficiently fast methods that can capture the structural changes of such transitions. Herein, a simple surfactant system consisting of sodium dodecyl sulfate (SDS) in aqueous NaCl solutions is investigated. Combining synchrotron radiation small‐angle X‐ray scattering (SAXS) with fast stopped‐flow mixing schemes allows monitoring the process where polymer‐like micelles are formed from globular micelles when the salt concentration is suddenly increased. The results show that “worm‐like” micelles are formed by fusion of globular micelles and short cylinders in a fashion that bears similarities to a step‐like polymerization process.     

Oxidative amidation of benzyl alcohols with amino acid esters mediated by N-hydroxysuccinimide/phenyliodine diacetate

A simple protocol involving metal-free oxidative amidation of benzyl alcohols with amino acid esters has been presented. The amidation proceeds in a radical pathway unlike in conventional metal-mediated extrusion of dihydrogen. The method is advantageous in terms of metal-free conditions, nonexpensive commercial starting substrates. Also various substituents in the starting materials are tolerated and sterically hindered amino acid side chains could provide good yields of amide products.     

A short and concise route to total synthesis of Dendrodolide L

A short and efficient method for the stereoselective synthesis of Dendrodolide L has been developed from inexpensive and commercially available starting material. This convergent synthesis utilizes Jacobsen kinetic resolution, regioselective ring-opening of epoxide and Yamaguchi macrolactonization as key steps.     

Enantioselective solvent-free Robinson annulation reactions

The enantioselective cyclization of the prochiral cyclic substrates1 to7 and26, can be carried out in theneat using S-proline as catalyst. The substrates18 to22 and27 could not be cyclized with S-proline but could be cyclized with a mixture of S-phenylalanine and d-camphorsulphonic acid. The enantioselective cyclization of prochiral acyclic triones45 and47 and also the racemic tricarbonyl compounds54 to57 could also be carried out in theneat using S-proline as catalyst. The optically active enediones obtained in the above cyclizations could also be obtained directly from 1,3-diones or 2-hydroxymethylene cycloalkanones in a one-pot reaction with methyl vinyl ketone (MVK) and S-proline in the absence of solvents.¹³C NMR studies of the one-pot synthesis ofS-11 andS-14 reveal that the annulations involve initial formation of an acid-base complex followed by a Michael reaction and then an enantioselective cyclization. Such enantioselective cyclizations probably occur on the surface of S-proline crystals.     

Large force fluctuations in a flowing granular medium

We study fluctuations in the force at the boundary of a 2D granular flow. The forces are mainly impulsive at all flow rates. The probability distribution of impulses decays exponentially at large impulses, as do the forces in a static granular medium. At small impulses, the distribution evolves continuously with flow rate with no indication of the transition from collisional flow to intermittently jamming flows. However, the distribution of the time interval between collisions tends to a power law, P(tau) - tau(-3/2), showing a clear dynamical signature of the approach to jamming.     

Electroactive, Internal Anthraquinonoid Dendritic Cores(1)

The modification of the extended 1 --> 3 anthraquinonoid monomer 1 by substitution of the central aliphatic moiety with a more rigid, aromatic moiety has allowed the syntheses of the new branched building block 6 possessing multiple, internal redox sites. This monomer was used to generate the first tier, dendritic macromolecules 8 and 9, which incorporate different internal redox centers within the infrastructure as well as the traditional peripheral multifunctionality. Using cyclic voltammetry experiments, the electrochemical response and electronic interactions between the two electroactive sites (the anthraquinonoid and nitroaromatic moieties) of these dendritic constructs were explored.     

Holographic moiré in real time

The body of knowledge necessary to observe holographic-moiré patterns in real time is introduced. The basic factors influencing fringe visibility in holographic moiré are analyzed and expressions to evaluate fringe visibility for any given displacement and deformation are given. The application of the introduced theory in the case of real-time observation is discussed. It is shown that the maximum benefits of this technique are achieved by combining it with closed-circuit TV. Several examples of application are given.     

Resonantly enhanced off-specular X-ray scattering from polymer/polymer interfaces<Superscript>⋆</Superscript>

We have used measurements of the absolute intensity of diffuse X-ray scattering to extract the interfacial tension of a buried polymer/polymer interface. Diffuse scattering was excited by an X-ray standing wave whose phase was adjusted to have a high intensity at the polymer/polymer interface and simultaneously a node at the polymer/air interface. This method permits the capillary-wave-induced roughness of the interface, and hence the interfacial tension, to be measured independently of the polymer/polymer interdiffusion.