Heterocyclic synthesis using ethyl carboethoxyformimidate

Ethyl carboethoxyformimidate is shown to be a versatile reagent for the synthesis of a variety of mono- and bicyclic heterocyclic systems.     

Crystals from concentrated glyme mixtures. The single-crystal structure of LiClO4

A procedure for the preparation of high-quality single crystals from concentrated glyme mixtures is presented. Anhydrous single crystals of LiNO(3) and LiClO(4) were prepared in this manner, and the single-crystal structure of LiClO(4) (orthorhombic, Pnma, a = 8.6447(12) A, b = 6.8512(10) A, c = 4.8254(7) A, Z = 4) was determined as an example. This procedure is expected to be widely applicable for not only salts but also a wide range of other materials solvated by glymes.     

A device for feline head positioning and stabilization during magnetic resonance imaging

Minimization of head movement and reproduction of standard head positions are essential for reliable brain functional magnetic resonance imaging. Devices for stabilization and alignment of feline preparations are not available currently. We describe a system that involves minimal surgery, allows for both acute and chronic atraumatic positioning, and has the potential to be used for unanesthetized animals. The device uses non-metallic materials and stabilizes the head by means of an apparatus that fixes the head with nylon screws and dental cement in the frontal sinuses. Application of the head-stabilizing device decreases head movements by more than a factor of ten. Anatomical images show that this device provides 3 dimensional head placement at a precision comparable to that of a stereotactic frame, i.e. within 1 mm.     

Gradient expansion of the atomic kinetic energy functional

It is demonstrated that the ground-state atomic kinetic energy functional T[?], where ? is the electron density, can be computed to surprising accuracy from the truncated gradient expansion: T[?] = + T₂[?] + T₄[?], with T_o[?] = $\text{3}\text{10}$(3π²)$\text{2}\text{3}$ ∫ ?$\text{5}\text{3}$ d_τ, T₂ [?] = $\text{1}\text{72}$ ∫ (??)²?^?1 d_τ, and T₄ [?] given by the formula of Hodges. Calculations of T₀, T₂ and T₄ are reported for He with ? both the Hartree—Fock and a very accurate density, and for Ne, Ar and Kr with ? the Hartree—Fock density. For Kr, T₀ + T₂ + T₄ is within 0.3% of the exact Hartree—Fock T, with T₂/T₀ = 0.05, T₄/T₂ = 0.17.     

Mechanism and Kinetics of Hexamethyldisilazane Reaction with a Fumed Silica Surface

An analytical study is presented on the thermocapillary migration of a fluid sphere within a constant applied temperature gradient in an arbitrary direction with respect to a plane surface. The Peclet and Reynolds numbers are assumed to be small so that the Laplace and Stokes equations, respectively, govern the temperature distributions and fluid velocities inside and outside the droplet. The asymptotic formulas for the temperature and the velocity fields in the quasi-steady situation are obtained by using a method of reflections. The plane surface can be a no-slip solid wall and/or a perfect-slip free surface. The boundary effect on the thermocapillary migration is found to be weaker than that on the motion driven by a body force. Even so, the interaction between the plane and the droplet can be very significant when the gap thickness approaches zero. For the motion of a droplet normal to a solid wall, the effect of the plane surface reduces the translational velocity of the droplet; however, this solid wall can be an enhancement factor on the particle migration as it is translating parallel to the wall. On the other hand, in case of a droplet migrating close to a free surface due to thermocapillarity, the droplet velocity can be either greater or smaller than that which would exist in the absence of the plane surface, depending on the relative thermal conductivity and the surface properties of the particle and its relative distance from the plane. Furthermore, the interacting thickness of the affected region by the presence of the plane is discussed by considering the droplet mobility. Generally speaking, a free surface exerts less influence on the particle movement than does a solid surface. Copyright 2000 Academic Press.     

Substitution reactions of [Fe(4)S(4)Cl(4)](2-) with Bu(t)NC or Et(2)NCS(2)(-): trapping intermediates and detecting new pathways

Kinetic studies on the substitution reaction between [Fe(4)S(4)Cl(4)](2-) and Bu(t)NC or Et(2)NCS(2)(-) are reported. The binding of small molecules and ions to Fe-S clusters is a fundamental step in substitution reactions but can be difficult to follow directly because these reactions are rapid and often associated with small spectroscopic changes. A novel kinetic method is reported which allows the time course of molecule and ion binding to Fe-S clusters to be followed by monitoring the lability of the cluster. Using a stopped-flow, sequential-mix apparatus, [Fe(4)S(4)Cl(4)](2-) and L (L = Et(2)NCS(2)(-) or Bu(t)NC) are rapidly mixed, and after a known time (delta) the resulting solution is mixed with a solution of PhS(-). The thiolate substitutes for the chloro ligands on the cluster, in a reaction which is easy to follow because of the large change in the visible absorption spectrum. The rate of this substitution is extremely sensitive to whether L is bound to the cluster or not. By correlation of delta with the rate of the reaction with PhS(-), the time course of the reaction between [Fe(4)S(4)Cl(4)](2-) and L can be mapped out. In studies where L = Bu(t)NC this technique has allowed the detection of an intermediate ([Fe(4)S(4)Cl(4)(CNBu(t))](2-)) which cannot be detected spectrophotometrically. In further studies, the substitution reactions of [Fe(4)S(4)Cl(4)](2-) with PhS(-), Et(2)NCS(2)(-), or Bu(t)NC are all perturbed by the addition of Cl(-). In all cases a common pathway for substitution is evident, but with Et(2)NCS(2)(-) an additional, slower pathway becomes apparent under conditions where the common pathway is completely inhibited by Cl(-).     

Liquid crystal oligomers: going beyond dimers

This review focuses on structure-property relationships in liquid crystal oligomers, which consist of molecules containing two or more mesogenic units linked via flexible spacers essentially in a linear fashion and so does not consider, for example, liquid crystal dendrimers and tetrapodes. Previous reviews have tended to focus mainly on liquid crystal dimers in which just two mesogenic units are interconnected by a single spacer. By contrast, this review is largely devoted to higher oligomers such as liquid crystal trimers and tetramers containing three or four mesogenic units connected by two or three spacers, respectively.     

Influence of Amide Connectivity on the Hydrogen-Bond-Directed Self-Assembly of [n.n]Paracyclophanes

Reported here is the synthesis and self-assembly characterization of [n.n]paracyclophanes ( [n.n]pCps , n=2, 3) equipped with anilide hydrogen bonding units. These molecules differ from previous self-assembling [n.n]paracyclophanes ( [n.n]pCps ) in the connectivity of their amide hydrogen bonding units (C-centered/carboxamide vs. N-centered/anilide). This subtle change results in a ≈30-fold increase in the elongation constant for the [2.2]pCp -4,7,12,15-tetraanilide ( [2.2]pCpNTA ) compared to previously reported [2.2]pCp -4,7,12,15-tetracarboxamide ( [2.2]pCpTA ), and a ≈300-fold increase in the elongation constant for the [3.3]pCp -5,8,14,17-tetraanilide ( [3.3]pCpNTA ) compared to previously reported [3.3]pCp -5,8,14,17-tetracarboxamide ( [3.3]pCpTA ). The [n.n]pCpNTA monomers also represent the reversal of a previously reported trend in solution-phase assembly strength when comparing [2.2]pCpTA and [3.3]pCpTA monomers. The origins of the assembly differences are geometric changes in the association between [n.n]pCpNTA monomers—revealed by computations and X-ray crystallography—resulting in a more favorable slipped stacking of the intermolecular π-surfaces ( [n.n]pCpNTA vs. [n.n]pCpTA ), and a more complementary H-bonding geometry ( [3.3]pCpNTA vs. [2.2]pCpNTA ).     

Salt,Shake, Fuse—Giant Hybrid Polymer/Lipid Vesicles through Mechanically Activated Fusion

Large (200 nm) poly(ethylene oxide)‐b‐poly(butadiene) polymer vesicles fuse into giant (>1 μm) vesicles with mild agitation in dilute aqueous NaCl solutions. This unusual effect is attributed to the salt‐induced contraction of the poly(ethylene oxide) corona, reducing steric resistance between vesicles and, with agitation, increasing the probability of contact between the hydrophobic cores of adjacent membranes. In addition, NaCl and agitation facilitated the creation of giant hybrid vesicles from much smaller homogeneous polymersomes and liposomes. Whereas lipid vesicles do not readily fuse with each other under the same circumstances, they did fuse with polymersomes to produce hybrid polymer/lipid vesicles.