Thermodynamic study of transthyretin association (wild‐type and senile forms) with heparan sulfate proteoglycan: pH effect and implication of the reactive histidine residue

The tetramer destabilization of transthyretin into monomers and its fibrillation are phenomena leading to amyloid deposition. Heparan sulfate proteoglycan (HSPG) has been found in all amyloid deposits. A chromatographic approach was developed to compare binding parameters between wild‐type transthyretin (wtTTR) and an amyloidogenic transthyretin (sTTR). Results showed a greater affinity of sTTR for HSPG at pH 7.4 compared with wtTTR owing to the monomeric form of sTTR. Analysis of the thermodynamic parameters showed that van der Waals interactions were involved at the complex interface for both transthyretin forms. For sTTR, results from the plot representing the number of protons exchanged vs pH showed that the binding mechanism was pH‐dependent with a critical value at a pH 6.5. This observation was due to the protonation of a histidine residue as an imidazolium cation, which was not accessible when TTR was in its tetrameric structure. At pH >6.5, dehydration at the binding interface and several contacts between nonpolar groups of sTTR and HSPG were also coupled to binding for an optimal hydrogen‐bond network. At pH <6.5, the protonation of the His residue from sTTR monomer when pH decreased broke the hydrogen‐bond network, leading to its destabilization and thus producing slight conformational changes in the sTTR monomer structure. Copyright © 2014 John Wiley & Sons, Ltd.     

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.     

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.     

Adaptive viewpoints for co-browsing on heterogeneous devices

Co-browsing is an activity in which a group of users navigate their way through of a set of Web pages together for a shared purpose. Effective co-browsing among users with different device capabilities requires a shared understanding of those Web pages. This paper demonstrates the concept of shared viewpoints (SVPs), and personal viewpoints (PVPs), for co-browsing, before detailing a framework for implementing these concepts. Finally, the effectiveness of the framework is presented through a perceptual experiment.     

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.     

Laterally coupled buried heterostructure high-Q ring resonators

All-buried InP-InGaAsP ring resonators laterally coupled to bus waveguides are demonstrated. The buried configurations offer a lower built-in refractive index step along the resonator periphery, which affords enhanced optical coupling coefficients between the waveguides and reduced scattering losses caused by the resonator sidewall imperfections. Very low optical intensity attenuations of 0.4 cm/sup -1/ and coupling-limited quality factors of greater than 10/sup 5/ are observed from 200-/spl mu/m-radii ring resonators. The measured spectral linewidth is as narrow as 0.0145 nm.