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.     

Chromophore-Free Sealing and Repair of Soft Tissues Using Mid-Infrared Light-Activated Biosealants

Poor strength, infection, leakage, long procedure times, and inflammation limit the efficacy of common tissue sealing devices in surgeries and trauma. Light-activated sealing is attractive for tissue sealing and repair, and can be facilitated by the generation of local heat following absorption of nonionizing laser energy by chromophores. Here, the inherent ability of biomaterials is exploited to absorb nonionizing, mid-infrared (midIR) light in order to engender rapid photothermal sealing and repair of soft tissue wounds. In this approach, the biomaterial simultaneously acts as a photothermal convertor as well as a biosealant, which dispenses the need for exogeneous light-absorbing nanoparticles or dyes. Biomechanical recovery, mathematical modeling, histopathology analyses, tissue strain mapping using digital imaging correlation, and visualization of the biosealant-tissue interface using hyperspectral imaging indicate superior performance of midIR sealing in live mice compared to conventional sutures and glue. The midIR-biosealant approach demonstrates rapid sealing of soft tissues, improves cosmesis, lowers potential for scarring, obviates safety concerns because of the nonionizing light used, and allows adoption of a wide diversity of biomaterials. Taken together, the studies demonstrate a novel advance both in biomaterials for surgical sealing along with the use of nonionizing midIR light, with high potential for clinical translation.     

General Formation of Macro-/Mesoporous Nanoshells from Interfacial Assembly of Irregular Mesostructured Nanounits

Mesoporous core–shell nanostructures with controllable ultra-large open channels in their nanoshells are of great interest. However, soft template-directed cooperative assembly to mesoporous nanoshells with highly accessible pores larger than 30 nm, or even above 50 nm into macroporous range, remains a significant challenge. Herein we report a general approach for precisely tailored coating of hierarchically macro-/mesoporous polymer and carbon shells, possessing highly accessible radial channels with extremely wide pore size distribution from ca. 10 nm to ca. 200 nm, on diverse functional materials. This strategy creates opportunities to tailor the interfacial assembly of irregular mesostructured nanounits on core materials and generate various core–shell nanomaterials with controllable pore architectures. The obtained Fe,N-doped macro-/mesoporous carbon nanoshells show enhanced electrochemical performance for the oxygen reduction reaction in alkaline condition.     

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.     

Frequency Insertion Strategy for Channel Assignment Problem

This paper presents a new heuristic method for quickly finding a good feasible solution to the channel assignment problem (CAP). Like many other greedy-type heuristics for CAP, the proposed method also assigns a frequency to a call, one at a time. Hence, the method requires computational time that increases only linear to the number of calls. However, what distinguishes the method from others is that it starts with a narrow enough frequency band so as to provoke violations of constraints that we need to comply with in order to avoid radio interference. Each violation is then resolved by inserting frequencies at the most appropriate positions so that the band of frequencies expands minimally. An extensive computational experiment using a set of randomly generated problems as well as the Philadelphia benchmark instances shows that the proposed method perform statistically better than existing methods of its kind and even yields optimum solutions to most of Philadelphia benchmark instances among which two cases are reported for the first time ever, in this paper. Won-Young Shin was born in Busan, Korea in 1978. He received B.S. in industrial engineering from Pohang University of Science and Technology (POSTECH) in 2001 and M.S in operation research and applied statistics from POSTECH in 2003. Since 2003 he has been a researcher of Agency for Defense Development (ADD) in Korea. He is interested in optimization of communication system and applied statistics. Soo Y. Chang is an associate professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He teaches linear programming, discrete optimization, network flows and operations research courses. His research interests include mathematical programming and scheduling. He has published in several journals including Discrete Applied Mathematics, Computers and Mathematics with Application, IIE Transactions, International Journal of Production Research, and so on. He is a member of Korean IIE, and ORMSS. Jaewook Lee is an assistant professor in the Department of Industrial Engineering at Pohang University of Science and Technology (POSTECH), Pohang, Korea. He received the B.S. degree in mathematics with honors from Seoul National University, and the Ph.D. degree from Cornell University in applied mathematics in 1993 and 1999, respectively. He is currently an assistant professor in the department of industrial engineering at the Pohang University of Science and Technology (POSTECH). His research interests include nonlinear systems, neural networks, nonlinear optimization, and their applications to data mining and financial engineering. Chi-Hyuck Jun was born in Seoul, Korea in 1954. He received B.S. in mineral and petroleum engineering from Seoul National University in 1977, M.S. in industrial engineering from Korea Advanced Institute of Science and Technology in 1979 and Ph.D. in operations research from University of California, Berkeley, in 1986. Since 1987 he has been with the department of industrial engineering, Pohang University of Science and Technology (POSTECH) and he is now a professor and the department head. He is interested in performance analysis of communication and production systems. He has published in several journals including IIE Transactions, IEEE Transactions, Queueing Systems and Chemometrics and Intelligent Laboratory Systems. He is a member of IEEE, INFORMS and ASQ.     

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.