In vivo three-dimensional spectral domain endoscopic optical coherence tomography using a microelectromechanical system mirror

A biopsy is a well-known medical test used to evaluate tissue abnormality. Biopsy specimens are invasively taken from part of a lesion and visualized by microscope after chemical treatment. However, diagnosis by means of biopsy is not only variable due to depth and location of specimen but may also damage the specimen. In addition, only a limited number of specimens can be obtained, thus, the entire tissue morphology cannot be observed. We introduce a three-dimensional (3-D) endoscopic optical biopsy via optical coherence tomography employing a dual-axis microelectromechanical system scanning mirror. Since this technique provides high-resolution, noninvasive, direct, and multiple visualization of tissue, it could function as a clinical biopsy with advanced performance. The device was integrated with a conventional endoscope and utilized to generate in vivo 3-D clinical images in humans and animals.     

Molecular deformation and free-solution electrophoresis of DNA-uncharged polymer conjugates at high field strengths: theoretical predictions Part 2: Stretching

DNA sequencing by electrophoresis can be dramatically sped up by overcoming the need for the sieving medium. Normally it is possible to separate DNA based on size in free solution; however, not end-labeled free-solution electrophoresis (ELFSE) uses a neutral drag-tag molecule to make it possible. In experiments to date, the drag-tag and DNA together form a random coil conformation; while with future generation drag-tags and high fields, deformation of this conformation may occur. In the first paper in this series we investigated the conditions under which the DNA and label become hydrodynamically distinct (or segregated), based on a theoretical approach developed for the electrophoresis of polyampholytes. In this paper we study further deformation wherein either the DNA and/or a polymeric label stretch. We show that deformation may dramatically improve the capabilities of ELFSE, especially when both the DNA and a polymeric drag-tag fully stretch; however, reaching these regimes will require extremely high field intensities, something that only microchip technologies may be able to achieve.     

Crystallization of silver carboxylates from sodium carboxylate mixtures

Silver carboxylates can be made by the reaction of silver nitrate and the corresponding sodium carboxylates. The length of the alkyl chain has a significant impact on the product behavior. In this study, 18, 20, and 22 carbon chains (stearate, arachidate, and behenate, respectively) have been selected. All three sodium carboxylates are very insoluble in water at room temperature. Solutions are obtained above the Krafft temperature, which precipitates lamellar crystals if cooled at the proper cooling rate. Depending on the chain length, metastable morphologies, such as vesicles and tiny fibers, can be seen consecutively before hexagonal plates form. The carboxylate with the shorter chain length reaches equilibrium more quickly. All three silver carboxylates also take on a lamellar structure. Small-angle X-ray scattering (SAXS) shows that the d spacing of the crystals increases as the chain length increases. Cryo-TEM illustrates that the crystallites are the result of micelle nucleation and micelle aggregation. In addition, the crystallization process in the presence of silver bromide nanocrystals has been investigated. In the initial stage, an epitaxial interface is formed between the silver carboxylate crystallites and the cubic silver bromide grains. Budlike and strandlike structures grow because of it. The consequent strand enclosure restrains the crystal growth, which reduces the size and changes the morphology of the crystals.     

Numerical continuation of degenerate homoclinic orbits in planar systems

In this paper we develop numerical algorithms for the continuationof degenerate homoclinic connections in planar systems. We considerthe case where the equilibrium point has zero trace and twocases of higher-order degeneracies. The method we propose isable to continue homoclinic connections of order up to codimension-four.Application of the algorithm to four examples supports its validityand demonstrates its usefulness.     

Gas-phase deprotonation of arylalkylamines. A collision-induced dissociation study

The collision-induced dissociation (CID) of deprotonated arylalkylamines of general formula R(1)C(6)H(4)CHR(2)CH(2)NR(3)(2) (where R(1) = H, OH, F or NO(2); R(2) = H or OH; R(3) = H or CH(3)) generated by negative chemical ionization with H(2)O and D(2)O as ionizing reagents, is discussed. The negative chemical ionization mass spectra show that, in the absence of a hydroxy group in the aromatic ring, deprotonation takes place at the benzylic position whereas the proton is lost from the OH group when present. The nitro compound forms only M(-.) ions. The CID spectra of the deprotonated molecules show that fragmentations are strongly dependent on the structural features of the molecules, namely the presence or absence of substituents in the aromatic ring or aliphatic chain. Copyright 1999 John Wiley & Sons, Ltd.     

The onset of coulomb explosions in polyatomic molecules

With the development of high intensity femtosecond lasers, the ionisation and dissociation dynamics of molecules has become an area of considerable interest. Using the technique of femtosecond laser mass spectrometry (FLMS), the molecules carbon disulphide, pyrimidine, toluene, cyclohexanone and benzaldehyde are studied with pulse widths of 50 fs in the near infrared (IR) wavelength region (790 nm). Results are presented and contrasted for laser beam intensities around 10(15) and 10(16) W cm(-2). For the lower intensities, the mass spectra yield dominant singly charged parent ions. Additionally, the appearance of doubly charged parent ions is evident for carbon disulphide, toluene and benzaldehyde with envelopes of doubly charged satellite species existing in these local regions. Carbon disulphide also reveals a small triply charged component. Such atomic-like features are thought to be a strong fingerprint of FLMS at these intensities. However, upon increasing the laser intensity to approximately 10(16) W cm(-2), parent ion dominance decreases and the appearance of multiply charged atomic species occurs, particularly carbon. This phenomenon has been attributed to Coulomb explosions in which the fast absorption of many photons may produce transient highly ionised parent species which can subsequently blow apart. Copyright 1999 John Wiley & Sons, Ltd.     

Uniform molecular analysis using femtosecond laser mass spectrometry

The potential of femtosecond laser time-of-flight mass spectrometry (FLMS) for uniform quantitative analysis of molecules has been investigated. Various samples of molecular gases and vapours have been studied, using ultra-fast ( approximately 50 fs) laser pulses with very high intensity (up to 1.6 x 10(16) Wcm(-2)) for non-resonant multiphoton ionisation/tunnel ionisation. Some of these molecules have high ionisation potentials, requiring up to ten photons for non-resonant ionisation. The relative sensitivity factors (RSF) have been determined as a function of the laser intensity and it has been demonstrated that for molecules with very different masses and ionisation potentials, uniform ionisation has been achieved at the highest laser intensities. Quantitative laser mass spectrometry of molecules is therefore a distinct possibility. Copyright 1999 John Wiley & Sons, Ltd.     

A simple decision model of counterproliferation

We develop a simple decision model of counterproliferation involving a status quo “incumbent” and a nuclear “entrant”. The problem is examined as a one-stage interaction in two phases: nuclear development and deployment. We examine the conditions that will influence the decision to move pre-emptively against a proliferator's nuclear program. Particular attention is given to the role of uncertainty in determining the expected costs of action at different points in the entrant's weapon's development and deployment cycle. The model permits us to determine the optimal time to act given varying levels of information concerning entrant behavior. In conclusion, we examine the tradeoffs between the expected costs of action and the costs of intelligence.     

Orbital analysis of bonding in diarylhalonium salts and relevance to periodic trends in structure and reactivity

Diarylhalonium compounds provide new opportunities as reagents and catalysts in the field of organic synthesis. The three center, four electron (3c–4e) bond is a center piece of their reactivity, but structural variation among the diarylhaloniums, and in comparison with other λ³-iodanes, indicates that the model needs refinement for broader applicability. We use a combination of Density Functional Theory (DFT), Natural Bond Orbital (NBO) Theory, and X-ray structure data to correlate bonding and structure for a λ³-iodane and a series of diarylchloronium, bromonium, and iodonium salts, and their isoelectronic diarylchalcogen counterparts. This analysis reveals that the s-orbital on the central halogen atom plays a greater role in the 3c–4e bond than previously considered. Finally, we show that our revised bonding model and associated structures account for both kinetic and thermodynamic reactivity for both acyclic phenyl(mesityl)halonium and cyclic dibenzohalolium salts.

A revised bonding model for diarylhalonium salts, that involves partial s-orbital contribution, provides new insight into periodic trends in structure and reactivity.     

Twisted Steinberg algebras

We introduce twisted Steinberg algebras over a commutative unital ring R. These generalise Steinberg algebras and are a purely algebraic analogue of Renault's twisted groupoid C*-algebras. In particular, for each ample Hausdorff groupoid G and each locally constant 2-cocycle σ on G taking values in the units $R^{\times }$, we study the algebra $A_R(G,\sigma )$ consisting of locally constant compactly supported R-valued functions on G, with convolution and involution “twisted” by σ. We also introduce a “discretised” analogue of a twist Σ over a Hausdorff étale groupoid G, and we show that there is a one-to-one correspondence between locally constant 2-cocycles on G and discrete twists over G admitting a continuous global section. Given a discrete twist Σ arising from a locally constant 2-cocycle σ on an ample Hausdorff groupoid G, we construct an associated twisted Steinberg algebra $A_R(G;\mathrm{\Sigma })$, and we show that it coincides with $A_R(G,{\sigma }^{?1})$. Given any discrete field ${\mathbb{F}}_d$, we prove a graded uniqueness theorem for $A_{{\mathbb{F}}_d}(G,\sigma )$, and under the additional hypothesis that G is effective, we prove a Cuntz–Krieger uniqueness theorem and show that simplicity of $A_{{\mathbb{F}}_d}(G,\sigma )$ is equivalent to minimality of G.