Induced Chiroptical Changes of a Water‐Soluble Cryptophane by Encapsulation of Guest Molecules and Counterion Effects

We report the synthesis of the water‐soluble cryptophanol derivative 1 and the study of the chiroptical properties of its two enantiomers (>99 % ee) by polarimetry, electronic circular dichroism (ECD), and vibrational circular dichroism (VCD). We show that cryptophanol 1 exhibits unusual chiroptical properties in water under basic conditions (pH>12). For instance, the shapes of the ECD and VCD spectra of 1 in water were strongly dependent on the nature of the alkali metal ions (Li⁺, Na⁺, K⁺, Cs⁺) surrounding the cryptophane and whether or not a guest molecule is present inside the cavity of the host. To the best of our knowledge, this is the first example in which the nature of these counterions governs the chiroptical properties of a host molecule. Moreover, specific ECD spectra were obtained depending on the size of the guest molecules. This makes 1 a good sensor for small neutral molecules in aqueous solvent. Finally, VCD experiments associated with DFT calculations show that the chiroptical changes can be directly correlated to the presence of charges close to the aromatic rings and with a conformational change of the alkyl chains upon encapsulation.     

Design and synthesis of novel ionic liquid/liquid crystals (ILCs) with axial chirality

As the first examples of axially chiral ionic liquids, new pyridinium salts having a 1,3-dioxan ring in their central core were synthesized. Enantioselective dehydrohalogenation using chiral alkoxides provided a simple and practical approach for their synthesis. Some structures exhibit both low melting point and liquid crystalline behaviour.     

Further results on the euler and Genocchi numbers

Summary We characterize the ordinary generating functions of the Genocchi and median Genocchi numbers as unique solutions of some functional equations and give a direct algebraic proof of several continued fraction expansions for these functions. New relations between these numbers are also obtained.     

A Java-based control system for the Orsay tandem accelerator

A new control system was designed for the tandem MP-9 at Orsay. Because of the existing devices located on high voltage platforms and the lack of space inside the accelerator, in-house electronic cards based on micro-controllers and an optical fieldbus were developed to collect data. VME processors under VxWorks, a real time operating system, manage the fieldbus, concentrate the accelerator information and transmit it to the supervisory software through the ethernet network. This software consists of a collection of Java virtual machines (JVM) running on several Unix work-stations and PCs under Windows. Some of the Java virtual machines manage apparatus, instruments, local display and connections to an object database and VME concentrators. Other manage general synoptics. JVMs communicate between themselves with RMI protocol and JRPC with VME concentrators. So the supervisory software can be spread over several control stations throughout the network.     

Déploiements non dicritiques des formes différentielles holomorphesA dx+B dy

Some special unfoldings of Pfaffian forms are studied. Applications to forms with small multiplicity are purposed.     

An improved approximation for the Rayleigh wave equation

We derive a simple expression, which gives an approximate value of the Rayleigh wave velocity in an isotropic solid. This approximation is five times better than that given by Viktorov. The velocity equation can be easily inverted in order to obtain an accurate determination of the elastic constants. This procedure can be worthwhile for elastic microanalysis of bulk materials by scanning acoustic microscopy.     

Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes

2,5‐Diferrocenyl‐1‐Ar‐1H‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐tert‐butylphenyl ( e )) have been prepared by reactions of ArPH₂ ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐tert‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [NnBu₄][B(C₆F₅)₄]; these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ]⁺–[ 3 e ]⁺ show intervalence charge‐transfer absorptions between 4650 and 5050 cm^?1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b .     

Evaluation of the evolution of relationships between topics over time

Topics that attract public attention can originate from current events or developments, might be influenced by situations in the past, and often continue to be of interest in the future. When respective information is made available textually, one possibility of detecting such topics of public importance consists in scrutinizing, e.g., appropriate press articles using—given the continual growth of information—text processing techniques enriched by computer routines which examine present-day textual material, check historical publications, find newly emerging topics, and are able to track topic trends over time. Information clustering based on content-(dis)similarity of the underlying textual material and graph-theoretical considerations to deal with the network of relationships between content-similar topics are described and combined in a new approach. Explanatory examples of topic detection and tracking in online news articles illustrate the usefulness of the approach in different situations.