Highly Selective Copper‐Catalyzed Asymmetric [3+2] Cycloaddition of Azomethine Ylides with Acyclic 1,3‐Dienes

The first examples of the catalytic asymmetric 1,3‐dipolar cycloaddition of azomethine ylides with acyclic activated 1,3‐dienes (and 1,3‐enynes) are described. Under copper catalysis, a selective cycloaddition at the terminal γ,δ‐C?C bond is observed. In addition, depending on the ligand used, either the exo or the endo adduct can be obtained with high selectivity. Under appropriate reaction conditions, the acyclic 1,6‐addition product is detected, suggesting a stepwise mechanism. The resulting C4‐alkenyl‐substituted pyrrolidines are suitable substrates for further access to polycyclic systems, as highlighted by the preparation of hexahydrochromeno[4,3‐b]pyrrole and the tetracyclic core of the alkaloid gracilamine.     

Beyond Stereoselectivity,Switchable Catalysis: Some of the Last Frontier Challenges in Ring‐Opening Polymerization of Cyclic Esters

Metal‐based catalysts and initiators have played a pivotal role in the ring‐opening polymerization (ROP) of cyclic esters, thanks to their high activity and remarkable ability to control precisely the architectures of the resulting polyesters in terms of molar mass, dispersity, microstructure, or tacticity. Today, after two decades of extensive research, the field is slowly reaching maturity. However, several challenges remain, while original concepts have emerged around new types or new applications of catalysis. This Review is not intended to comprehensively cover all of these aspects. Rather, it provides a personal overview of the very recent progress achieved in some selected, important aspects of ROP catalysis—stereocontrol and switchable catalysis. Hence, the first part addresses the development of new metal‐based catalysts for the isoselective ROP of racemic lactide towards stereoblock copolymers, and the use of syndioselective ROP metal catalysts to control the monomer sequence in copolymers. A second part covers the development of ROP catalysts—primarily metal‐based catalysts, but also organocatalysts—that can be externally regulated by the use of chemical or photo stimuli to switch them between two states with different catalytic abilities. Current challenges and opportunities are highlighted.     

GDME-based methodology for the determination of free formaldehyde in cosmetics and hygiene products containing formaldehyde releasers

Analytical and Bioanalytical Chemistry - Formaldehyde is often applied in the industrial production of different products, such as textiles, insulation materials, or cosmetics, due to its...     

Small‐Sized High‐Power PIN Diode Switch with Defected Ground Structure for Wireless Broadband Internet

This letter presents a small‐sized, high‐power single‐pole double‐throw (SPDT) switch with defected ground structure (DGS) for wireless broadband Internet application. To reduce the circuit size by using a slow‐wave characteristic, the DGS is used for the quarter‐wave (°/4) transmission line of the switch. To secure a high degree of isolation, the switch with DGS is composed of shunt‐connected PIN diodes. It shows an insertion loss of 0.8 dB, an isolation of 50 dB or more, and power capability of at least 50 W at 2.3 GHz. The switch shows very similar performance to the conventional shunt‐type switch, but the circuit size is reduced by about 50% simply with the use of DGS patterns.     

An MPEG‐4 Compliant Interactive Multimedia Streaming Platform Using Overlay Networks

This paper presents a multimedia streaming platform for efficiently transmitting MPEG‐4 content over IP networks. The platform includes an MPEG‐4 compliant streaming server and client, supporting object‐based representation of multimedia scenes, interactivity, and advanced encoding profiles defined by the ISO standard. For scalability purposes, we employ an application‐layer multicast scheme for media transmission using overlay networks. The overlay network, governed by the central entity of the network distribution manager, is dynamically deployed according to a set of pre‐defined criteria. The overlay network supports both broadcast delivery and video‐on‐demand content. The multimedia streaming platform is standards‐compliant and utilizes widespread multimedia protocols such as MPEG‐4, real‐time transport protocol, real‐time transport control protocol, and real‐time streaming protocol. The design of the overlay network was architected with the goal of transparency to both the streaming server and the client. As a result, many commercial implementations that use industry‐standard protocols can be plugged into the architecture relatively painlessly and can enjoy the benefits of the platform.     

On the Feasibility of Growing Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 Single Crystals

Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZNT91/9) single crystals were grown by two methods: from solution using PbO as a self‐fluxing agent (SC method) and directly from the melt without fluxing (MC method). In both growth methods, an allomeric Pb[(Mg_1/3‐Nb_2/3)_0.69Ti_0.31]O₃ (PMNT69/31) single crystal was used as a seed. X‐ray diffraction patterns of ground crystals showed that phase‐pure perovskite PZNT91/9 single crystals were successfully fabricated by the above two methods. The composition of the crystals obtained by both the SC and MC methods was analyzed using X‐ray fluorescence, which confirmed that the crystal composition is close to the nominal value, although volatilization of PbO and segregation during crystal growth are inevitable. The MC PZNT91/9 crystals exhibit excellent piezoelectric properties, with the piezoelectric constant, d₃₃, in the range of 1800–2200 pC N^–1. This value is comparable to that of the SC crystals. However, the MC crystals show an abnormal dielectric behavior. In contrast with the SC crystals, in the MC crystals a much broader dielectric peak appears in the dielectric response curves, accompanied by a much lower peak temperature of around 105 °C. Furthermore, frequency dispersion is apparent over a much wider temperature range (even more apparent than in pure relaxors), where a large, i.e., about 70 °C, full width at half maximum (FWHM) for the dielectric peaks is observed in the dielectric response. It is speculated that such an unusual phenomenon correlates with defects, microinhomogeneities, and polar regions in the as‐grown MC crystals. The origins of this abnormality have not been interpreted in detail until now. However, optical observation of the domain structure confirms that both the SC and MC crystals possess complex structural states.     

A Donor–Acceptor Polymer with a Peculiar Negative‐Charge‐“Trapping” Characteristic

Voltammetric and spectrophotometric measurements of poly(3,3″‐dipentoxy‐3′‐dicyanoethenyl‐2,2′:5′,2″‐terthiophene) (polyCN) films, in connection with other experimental evidence, reveal a normal oxidative, but a peculiar reductive behavior consisting of trapping of the negative charge during the cathodic scan. Another interesting property of polyCN films is the tendency to form strong intramolecular and intermolecular associations, probably charge‐transfer (CT) complexes. These properties could account for the fact that the photovoltaic performance does not improve when polyCN is blended with a polythiophene donor.