Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3](infinity) coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.

Modelling relative motion to facilitate intra-limb coordination

The importance of relative motion information when modelling a novel motor skill was examined. Participants were assigned to one of four groups. Groups 1 and 2 viewed demonstrations of a skilled cricket bowler presented in either video or point light format. Group 3 observed a single point of light pertaining to the wrist of the skilled bowler only. Participants in Group 4 did not receive a demonstration and acted as controls. During 60 acquisition trials, participants in the demonstration groups viewed a model five times before each 10-trial block. Retention was examined the following day. Intra-limb coordination was assessed for the right elbow relative to the wrist in comparison to the model. The demonstration groups showed greater concordance with the model than the control group. However, the wrist group performed less like the model than the point light and video groups, who did not differ from each other. These effects were maintained in retention. Relative motion information aided the acquisition of intra-limb coordination, while making this information more salient (through point lights) provided no additional benefit. The motion of the models bowling arm was replicated more closely than the non-bowling arm, suggesting that information from the end-effector is prioritized during observation for later reproduction.

Generic SoC QR Array Processor for Adaptive Beamforming

A generic architecture for implementing a QR array processor in silicon is presented. This improves on previous research by considerably simplifying the derivation of timing schedules for a QR system implemented as a folded linear array, where account has to be taken of processor cell latency and timing at the detailed circuit level. The architecture and scheduling derived have been used to create a generator for the rapid design of System-on-a-Chip (SoC) cores for QR decomposition. This is demonstrated through the design of a single-chip architecture for implementing an adaptive beamformer for radar applications. Published as IEEE Trans Circuits and Systems Part II, Analog and Digital Signal Processing, April 2003 NOT Express Briefs. Parts 1 and II of Journal reorganised since then into Regular Papers and Express briefs

Application-Specific Instruction Set Processor for SoC implementation of Modern Signal Processing Algorithms

A novel application-specific instruction set processor (ASIP) for use in the construction of modern signal processing systems is presented. This is a flexible device that can be used in the construction of array processor systems for the real-time implementation of functions such as singular-value decomposition (SVD) and QR decomposition (QRD), as well as other important matrix computations. It uses a coordinate rotation digital computer (CORDIC) module to perform arithmetic operations and several approaches are adopted to achieve high performance including pipelining of the micro-rotations, the use of parallel instructions and a dual-bus architecture. In addition, a novel method for scale factor correction is presented which only needs to be applied once at the end of the computation. This also reduces computation time and enhances performance. Methods are described which allow this processor to be used in reduced dimension (i.e., folded) array processor structures that allow tradeoffs between hardware and performance. The net result is a flexible matrix computational processing element (PE) whose functionality can be changed under program control for use in a wider range of scenarios than previous work. Details are presented of the results of a design study, which considers the application of this decomposition PE architecture in a combined SVD/QRD system and demonstrates that a combination of high performance and efficient silicon implementation are achievable. © 2005 IEEE.

WLAN Security Processor

A novel wireless local area network (WLAN) security processor is described in this paper. It is designed to offload security encapsulation processing from the host microprocessor in an IEEE 802.11i compliant medium access control layer to a programmable hardware accelerator. The unique design, which comprises dedicated cryptographic instructions and hardware coprocessors, is capable of performing wired equivalent privacy, temporal key integrity protocol, counter mode with cipher block chaining message authentication code protocol, and wireless robust authentication protocol. Existing solutions to wireless security have been implemented on hardware devices and target specific WLAN protocols whereas the programmable security processor proposed in this paper provides support for all WLAN protocols and thus, can offer backwards compatibility as well as future upgrade ability as standards evolve. It provides this additional functionality while still achieving equivalent throughput rates to existing architectures. © 2006 IEEE.

CORDIC based application-specific instruction set processor for QRD/SVD

An application specific programmable processor (ASIP) suitable for the real-time implementation of matrix computations such as Singular Value and QR Decomposition is presented. The processor incorporates facilities for the issue of parallel instructions and a dual-bus architecture that are designed to achieve high performance. Internally, it uses a CORDIC module to perform arithmetic operations, with pipelining of the internal recursive loop exploited to multiplex the two independent micro-rotations onto a single piece of hardware. The net result is a flexible processing element whose functionality can be changed under program control, which combines high performance with efficient silicon implementation. This is illustrated through the results of a detailed silicon design study and the applications of the techniques to a combined SVD/QRD system.

Performance analysis of an improved power-saving medium access protocol for IEEE 802.11 point coordination function WLAN

Wireless enabled portable devices must operate with the highest possible energy efficiency while still maintaining a minimum level and quality of service to meet the user's expectations. The authors analyse the performance of a new pointer-based medium access control protocol that was designed to significantly improve the energy efficiency of user terminals in wireless local area networks. The new protocol, pointer controlled slot allocation and resynchronisation protocol (PCSAR), is based on the existing IEEE 802.11 point coordination function (PCF) standard. PCSAR reduces energy consumption by removing the need for power saving stations to remain awake and listen to the channel. Using OPNET, simulations were performed under symmetric channel loading conditions to compare the performance of PCSAR with the infrastructure power saving mode of IEEE 802.11, PCF-PS. The simulation results demonstrate a significant improvement in energy efficiency without significant reduction in performance when using PCSAR. For a wireless network consisting of an access point and 8 stations in power saving mode, the energy saving was up to 31% while using PCSAR instead of PCF-PS, depending upon frame error rate and load. The results also show that PCSAR offers significantly reduced uplink access delay over PCF-PS while modestly improving uplink throughput.

Identical extraction behavior and coordination of trivalent or hexavalent f-element cations using ionic liquid and molecular solvents

The extraction of both UO22+ and trivalent lanthanide and actinide ions (Am3+, Nd3+, Eu3+) by dialkylphosphoric or dialkylphosphinic acids from aqueous solutions into the ionic liquid, 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide has been studied and compared to extractions into dodecane. Radiotracer partitioning measurements show comparable patterns of distribution ratios for both the ionic liquid/aqueous and dodecane/aqueous systems, and the limiting slopes at low acidity indicate the partitioning of neutral complexes in both solvent systems. The metal ion coordination environment, elucidated from EXAFS and UV-visible spectroscopy measurements, is equivalent in the ionic liquid and dodecane solutions with coordination of the uranyl cation by two hydrogen-bonded extractant dimers, and of the trivalent cations by three extractant dimers. This is the first definitive report of a system where both the biphasic extraction equilibria and metal coordination environment are the same in an ionic liquid and a molecular organic solvent.