Crystal structure of a non-stoichiometric channel inclusion complex of 1-benzyl-6-phenylpiperidin-2-one-5-carboxylic acid with acetonitrile

C₁₉H₁₉NO₃·x CH₃CN (x=0.3),M _r=643.35, hexagonal, space groupP6₁ (No. 169),a=23.027(5),c=5.775(1) Å,V=2652(1) ų,Z=6. The structure was solved by direct methods and refined toR=0.077 for 1562 observed MoK reflections. The title heterocyclic carboxylic acid was established as thetrans isomer, with the phenyl and carboxyl substituents occupying pseudo-equatorial and equatorial positions, respectively, of the piperidin-2-one ring in a half-chair conformation. Acid host molecules related by the 6₁ screw operation are linked by intermolecular O–H...O (cyclic amide) hydrogen bonds to generate an open channel bounded by coaxial intertwined helices each having a pitch of 5c. Within each channel of free diameterca. 6.0 Å the acetonitrile molecules partially occupy highly disordered sites which do not lie on thec axis. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82067 (13 pages).     

Synthesis of Thiophene‐Based π‐Conjugated Oligomers via Ligand‐Enabled Pd‐Catalyzed Suzuki–Miyaura Coupling of Haloterthienyls

A ligand‐enabled Pd‐catalyzed Suzuki–Miyaura coupling of haloterthienyls for the synthesis of various thiophene‐based π‐conjugated oligomers including quinquethiophenes is demonstrated. An indolyl phosphine ligand plays an important role in this transformation. Thiopheneboronic acids were well applied, which might open up a window for the application of thiopheneboronic acids in the synthesis of thiophene‐based π‐conjugated oligomers in materials chemistry.     

MESO-SUBSTITUTION REACTION OF ZINC OCTAETHYLPORPHYRIN VIA ANODIC OXIDATION

meso-Nitration, chlorination and acetoxylation of ZnOEP viaanodic oxidation are reported to proceed via EE'C, ECE and EE'C mechanismrespectively.     

Semilinear elliptic problems in annular domains

The method of shooting is used to establish existence of positive radially symmetric solutions to nonlinear elliptic equations of the form u+f(r, u)=0 on annular regionsa<r=|x|<b inR ^N , satisfying Dirichlet or Neumann conditions on the boundary. This extends recent work done by Bandle, Coffman and Marcus. A result concerning uniqueness of such solutions is also extended.

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Zusammenfassung Mit Hilfe eines Schiessverfahrens wird die Existenz von Lösungen nichtlinearer Probleme der Form u+f(r, u)=0 in ringförmigen Gebieten nachgewiesen, die verschiedenen Randbedingungen genügen. Es wird auch ihre Eindeutigkeit untersucht. Diese Arbeit verallgemeinert gewisse Ergebnisse von Bandle, Coffman und Marcus.

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Résumé On utilise une méthode de tir pour établir l'existence de solutions de problèmes non linéaires du type u+f(r, u)=0 dans des anneaux, vérifiant différentes conditions aux limites. Ensuite on discute l'unicité de ces solutions. Ce travail généralise certains résultats de Bandle, Coffman et Marcus.

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This work was supported by the Applied Mathematical Sciences subprogram of the Office of Energy Research, U.S. Department of Energy, under contract W-31-109-Eng-38. The author also wants to thank the Mathematics Institute, University of Basel, for supporting a visit in Oct., 1987 during which the project was initiated.     

Regio- and enantioselective intermolecular rhodium-catalyzed [2+2+2] carbocyclization reactions of 1,6-enynes with methyl arylpropiolates

Transition metal-catalyzed [m+n+o] carbocyclization reactions provide powerful methods for the construction of complex polycyclic systems that are generally not accessible through classical pericyclic reactions. We have developed the first regio- and enantioselective crossed intermolecular rhodium-catalyzed [2+2+2] carbocyclization of carbon- and heteroatom-tethered 1,6-enynes with unsymmetrical 1,2-disubstituted alkynes. This study clearly delineates the ligand requirements for obtaining excellent regio- and enantioselectivity. Furthermore, the ability to utilize various electron-withdrawing groups, and to introduce quaternary carbon stereogenic centers, provides the level of versatility necessary for its application to target-directed synthesis. Additional studies on the development and application of this novel methodology to the total synthesis of natural products are currently underway.     

Label-free cell separation and sorting in microfluidic systems

Cell separation and sorting are essential steps in cell biology research and in many diagnostic and therapeutic methods. Recently, there has been interest in methods which avoid the use of biochemical labels; numerous intrinsic biomarkers have been explored to identify cells including size, electrical polarizability, and hydrodynamic properties. This review highlights microfluidic techniques used for label-free discrimination and fractionation of cell populations. Microfluidic systems have been adopted to precisely handle single cells and interface with other tools for biochemical analysis. We analyzed many of these techniques, detailing their mode of separation, while concentrating on recent developments and evaluating their prospects for application. Furthermore, this was done from a perspective where inertial effects are considered important and general performance metrics were proposed which would ease comparison of reported technologies. Lastly, we assess the current state of these technologies and suggest directions which may make them more accessible.