Orientation imaging microscopy in two-dimensional crystals via undersampled microscopy

A novel microscopy analysis technique is presented, with applications in imaging two-dimensional grains and grain boundaries. The method allows the identification of grain shapes and orientations from large area micrographs, via the moiré pattern obtained in a raster image. The observed moiré pattern originates from the aliasing between a micrographs regular sampling raster and the inherent periodicity of the elements forming the grain under study. The technique presented is very general, allowing grain analysis via many types of microscopy. We demonstrate it in this paper by using Tapping Mode Atomic Force Microscopy and Scanning Electron Microscopy on diblock copolymer thin films. PACS 68.37.Ps; 68.37.Hk; 68.37.Ef; 68.55.Jk; 61.72.Ff; 61.72.Mm     

Ultrasonic pulsed Doppler transoesophageal measurement of aortic haemodynamics in humans.

Centreline blood velocity and exterior wall motion were measured in the descending aorta of humans using an oesophageal probe, a pulsed ultrasound Doppler velocity meter and an ultrasonic echo tracking system. The development of a method for easily measuring haemodynamics in the thoracic region using an oesophageal probe will provide an essentially non-invasive method for the assessment of cardiac function and the nature of blood vessels in that region. Detailed anatomical studies of the thorax were conducted by cross-sectioning of the thorax of a cadaver. Blood velocity waveforms were recorded from the descending aorta both during rest and exercise. In one volunteer, the peak centreline velocity increased from a resting value of approximately 30 cm s-1 to an exercise value of approximately 50 cm s-1. Vessel diameter waveforms similar to those for pressure were also recorded showing diameter changes of 1.8 mm. The accuracy and resolution of the technique would be improved by multicrystal probes and multigate ultrasonic flowmeters allowing for accurate calculation of the Doppler angle, imaging of vascular flow regions, and measurement of pulse wave velocity.     

Regiodirected phosphorylation of 2,2′,7,7′-tetrahydroxydinaphthylmethane

The phosphorylation of 2,2′,7,7′-tetrahydroxydinaphthylmethane was studied and the influence of molecule pre-organization on the regioselectivity of functionalization was investigated. The reactions of 2,2′,7,7′-tetrahydroxydinaphthylmethane with phosphorous amides containing 1-3 amide bonds gave oligophosphorylated derivatives differing in the number and the nature of phosphorus fragments and in the size of phosphorus rings: tetraphosphorus macrocycles containing one 24-membered and two eight-membered phosphorus rings, triphosphorus compounds containing a phosphocine ring and two acyclic phosphorus fragments, and tetraphosphorylated derivatives with four phosphorus groups in the molecule. The possibility of controlling the regioselectivity of phosphorylation by using reagents differing in the number and activity of P-N bonds was demonstrated.     

How noise statistics impact models of enzyme cycles

Theoretical tools for adequately treating stochastic effects are important for understanding their role in biological processes. Although master equations provide rigorous means for investigating effects associated with fluctuations of discrete molecular copy numbers, they can be very challenging to treat analytically and numerically. Approaches based on the Langevin approximation are often more tractable, but care must be used to ensure that it is justified in each situation. Here, we examine a model of an enzyme cycle for which noise qualitatively alters the behavior of the system: fluctuations in the population of an enzyme can result in amplification and multistability in the distribution of its product. We compare master equation and Langevin treatments of this system and show that results derived previously with a white noise Langevin equation [M. Samoilov et al., Proc. Natl. Acad. Sci. U.S.A. 102, 2310 (2005)] are inconsistent with the master equation. A colored noise Langevin equation captures some, but not all, of the essential physics of the system. The advantages and disadvantages of the Langevin approximation for modeling biological processes are discussed.     

Direct imaging of polyethylene crystallites within block copolymer microdomains

Ruthenium tetroxide (RuO₄) is a versatile agent for imparting mass density contrast to saturated hydrocarbon polymers. We have successfully employed RuO₄ to examine the microdomain and crystallite morphologies of poly(ethylene‐block‐vinylcyclohexane) semicrystalline–glassy diblock copolymers via transmission electron microscopy (TEM). Ultrathin sections cut from blocks stained with RuO₄ showed excellent contrast in TEM, revealing the individual polyethylene crystallites that formed within the preexisting block copolymer microdomains. The size and orientation of the crystallites, which previously could only be inferred from scattering data, are readily apparent in the micrographs. Moreover, such imaging directly reveals the lateral extent of the crystallites and the number of crystallites lying within the cross section of each microdomain. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2564–2570, 2000     

Self-Assembly of Chiral Cyclohexanohemicucurbit[n]urils with Bis(Zn Porphyrin): Size,Shape, and Time-Dependent Binding

In order to investigate the ability of bis(zinc octaethylporphyrin) (bis–ZnOEP) to discriminate cyclohexanohemicucurbit[n]urils (cycHC[n]) of different shapes and sizes, the self-assembly of barrel-shaped chiral cycHC[n] with bis–ZnOEP was studied by various spectroscopic methods (absorption, fluorescence, circular dichroism (CD), and NMR). While the binding of 6-membered cycHC[6] induced a tweezer-like conformation followed by the formation of anti-form of bis–ZnOEP upon further addition of cycHC[6], the interaction of 8-membered cycHC[8] is more complex and proceeds through the featured syn-to-anti conformational change of bis–ZnOEP and further intermolecular self-assembly via multiple noncovalent associations between cycHC[8] and bis–ZnOEP. Whilst bis–porphyrins are known to be effective chemical sensors able to differentiate various guests based on their chirality via induced CD, their ability to sense small differences in the shape and size of relatively large macrocycles, such as chiral cycHC[6] and cycHC[8], is scarcely examined. Both studied complexes exhibited characteristic induced CD signals in the region of porphyrin absorption upon complexation.