Anionic iron(II) alkoxides as initiators for the controlled ring‐opening polymerization of lactide

Hetero‐bimetallic Fe(II) alkoxide/aryloxides were evaluated as initiators for the ring‐opening polymerization of rac‐lactide. [(THF)NaFe(O^tBu)₃]₂ ( 1 ) and [(THF)₄Na₂Fe(2,6‐diisopropylphenolate)₄] ( 2 ) (THF = tetrahydrofuran) both polymerized lactide efficiently at room temperature, with complex 1 affording better control over the molecular weight parameters of the resultant polymer. At conversions below 70%, a linear increase in molecular weight with conversion was observed, indicative of a well‐controlled polymerization process. Complex 2 is the first example of a dianionic Fe(II) alkoxide and has been structurally characterized to reveal a distorted square planar FeO₄ array in which both Na counterions bridge two aryloxide ligands and are further complexed by two THF ligands. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3798–3803, 2003     

Förster energy transfer from poly(arylene–ethynylene)s to an erbium–porphyrin complex

We study the infrared emission at 1.54 μm of an organolanthanide complex, Er(III)-tetraphenylporphyrin [Er(TPP)acac], both as a result of direct optical excitation and via energy transfer from host π-conjugate polymers of type poly(arylene–ethynylene) [PAE]. In the first case, the emission of the neat complex is characterized in inert transparent materials and a value of the quantum yield at 1.54 μm φ_IR=4×10⁻⁴ is measured. Then, fluorescence resonance transfer is investigated in blends of Er(TPP)acac with PAEs by monitoring the quenching of the polymer fluorescence along with the enhancement of both the visible emission of the ligand and the near-infrared band of Er³⁺. These different procedures allow a detailed analysis of the transfer efficiency within a specific implementation of the Förster model for polymeric donors. The experimental values of the critical radius R₀, ranging from 1.3 to 2.5 nm for the different blends, are in good agreement with theory for a wide interval of the physical and spectroscopic parameters. This suggests that other mechanisms for excitation transfer do not play a significant role in these materials.     

Sulfobetaine‐containing diblock and triblock copolymers via reversible addition‐fragmentation chain transfer polymerization in aqueous media

A novel bifunctional acrylamido‐based reversible addition–fragmentation chain transfer (RAFT) chain‐transfer agent (CTA), N,N′‐ethylenebis[2‐(thiobenzoylthio)propionamide] (CTA2), has been synthesized and used for the controlled free‐radical polymerization of N,N‐dimethylacrylamide (DMA). A comparative study of CTA2 and the monofunctional CTA N,N‐dimethyl‐s‐thiobenzoylthiopropionamide (CTA1) has been conducted. Polymerizations mediated by CTA1 result in poly(N,N‐dimethylacrylamide) (PDMA) homopolymers with unimodal molecular weight distributions, whereas CTA2 yields unimodal, bimodal, and trimodal distributions according to the extent of conversion. The multimodal nature of the PDMAs has been attributed to termination events and/or chains initiated by primary radicals. The RAFT polymerization of DMA with CTA2 also results in a prolonged induction period that may be attributed to the higher local concentration of dithioester functionalities early in the polymerization. A series of ω‐ and α,ω‐dithioester‐capped PDMAs have been prepared in organic media and subsequently employed as macro‐CTAs for the synthesis of diblock and triblock copolymers in aqueous media with the zwitterionic monomer 3‐[2‐(N‐methylacrylamido)‐ethyldimethylammonio] propane sulfonate (MAEDAPS). Additionally, an ω‐dithioester‐capped MAEDAPS homopolymer has been used as a macro‐CTA for the block polymerization of DMA. To our knowledge, this is the first example of a near‐monodisperse, sulfobetaine‐containing block copolymer prepared entirely in aqueous media. The diblock and triblock copolymers form aggregates in pure water that can be dissociated by the addition of salt, as determined by ¹H NMR spectroscopy and dynamic light scattering. In pure water, highly uniform, micellelike aggregates with hydrodynamic diameters of 71–93 nm are formed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1262–1281, 2003     

Investigation into the ROMP copolymerization of peptide‐ and PEG‐functionalized norbornene derivatives

The ring‐opening metathesis polymerizations (ROMP), using RuCl₂ (PCy₃)₂CHPh, of a series of peptide‐functionalized norbornene derivatives have been investigated. Incorporation of a PEG‐monomer was found to prevent premature precipitation of polymer strands during the course of polymerization reactions and yield water compatible polymers in high conversions. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3178–3190, 2007     

Driving Mechanisms of Delamination Related Reliability Problems in Exposed Pad Packages

Exposed pad packages were introduced in the late 1980s and early 1990s because of their excellent thermal and electrical performance. Despite these advantages, the exposed pad packages experience a lot of thermo-hygro-mechanical related reliability problems during qualification and testing. Examples are die lift, which occurs predominantly after moisture sensitivity level conditions, and die-attach to leadframe delamination leading to downbond stitch breaks during temperature cycling. In this chapter, nonlinear finite element (FE) models using fracture mechanics based J-integral calculations are used to assess the reliability problems of the exposed pad package family. Using the parametric FE models any geometrical and material effects can be explored to their impact on the occurrence diepad delamination, and dielift. For instance the impact of diepad size is found to be of much less importance as the impact of die thickness is. Using the fracture mechanics approach, the starting location for the delamination from thermo-hygro-mechanical point of view is deducted. The results indicate that when diepad delamination is present, cracks are likely to grow beneath the die and dielift will occur. The interaction between dielift and other failure modes, such as lifted ball bonds, are not found to be very significant. The FE models are combined with simulation-based optimization methods to deduct design guidelines for optimal reliability of the exposed pad family.     

Miniature in vivo robots for remote and harsh environments

Long-term human space exploration will require contingencies for emergency medical procedures including some capability to perform surgery. The ability to perform minimally invasive surgery (MIS) would be an important capability. The use of small incisions reduces surgical risk, but also eliminates the ability of the surgeon to view and touch the surgical environment directly. Robotic surgery, or telerobotic surgery, may provide emergency surgical care in remote or harsh environments such as space flight, or extremely forward environments such as battlefields. However, because current surgical robots are large and require extensive support personnel, their implementation has remained limited in forward environments, and they would be difficult, or impossible, to use in space flight or on battlefields. This paper presents experimental analysis of miniature fixed-base and mobile in vivo robots to support MIS surgery in remote and harsh environments. The objective is to develop wireless imaging and task-assisting robots that can be placed inside the abdominal cavity during surgery. Such robots will provide surgical task assistance and enable an on-site or remote surgeon to view the surgical environment from multiple angles. This approach is applicable to long-duration space flight, battlefield situations, and for traditional medical centers and other remote surgical locations.     

Inter-vehicle communication systems: a survey

Inter-vehicle communication (IVC) systems (i.e., systems not relying on roadside infrastructure) have the potential to radically improve the safety, efficiency, and comfort of everyday road travel. Their main advantage is that they bypass the need for expensive infrastructure; their major drawback is the comparatively complex networking protocols and the need for significant penetration before their applications can become effective. In this article we present several major classes of applications and the types of services they require from an underlying network. We then proceed to analyze existing networking protocols in a bottom-up fashion, from the physical to the transport layers, as well as security aspects related to IVC systems. We conclude the article by presenting several projects related to IVC as well as a review of common performance evaluation techniques for IVC systems.     

Modeling wireless fading channels via stochastic differential equations: identification and estimation based on noisy measurements

This paper is concerned with modeling and identification of wireless channels using noisy measurements. The models employed are governed by stochastic differential equations (SDEs) in state space form, while the identification method is based on the expectation-maximization (EM) algorithm and Kalman filtering. The algorithm is tested against real channel measurements. The results presented include state space models for the channels, estimates of inphase and quadrature components, and estimates of the corresponding Doppler power spectral densities (DPSDs), from sample noisy measurements. Based on the available measurements, it is concluded that state space models of order two are sufficient for wireless flat fading channel characterization.     

Global Asymptotical Synchronization of Chaotic Lur'e Systems Using Sampled Data: A Linear Matrix Inequality Approach

Sampled-data feedback control for master-slave synchronization schemes that consist of identical chaotic Lur'e systems is studied. Sufficient conditions for global asymptotic synchronization of such chaotic Lur'e systems are obtained using the free-weighting matrix approach and expressed in terms of linear matrix inequalities (LMIs). With the help of the LMI solvers, the sampled-data feedback control law can easily be obtained to globally asymptotically synchronize Lur'e chaotic systems. The effectiveness of the proposed method is finally illustrated via numerical simulations of chaotic Chua's circuits.     

Grouped Approach for the Design of H.264/AVC Motion Estimation Architectures

This letter presents a novel approach for organizing computational resources into groups within H.264/AVC motion estimation architectures, leading to reductions of up to 75% in the equivalent gate count with respect to state‐of‐the‐art designs.