Mössbauer spectroscopy evidence for reductive loss of bromine from C60Br24 in reactions of halogenated C60 with ferrocene

Reactions of ferrocene (C₅H₅)₂Fe with halogenated fullerenes C₆₀X _n for X=F, Cl, Br andn = 15–39) yield non-stoichiometric solids with intense singlet Mössbauer spectra characteristic of Cp₂Fe₊ (where Cp=C₅H₅). The material isolated from reaction of Cp₂Fe with C₆₀Br₂₄ exhibits two different iron environments and magnetic ordering temperatures of 14 K and between 4.6 and 1.32 K. These data are seen to be consistent with loss of bromine from the fullerene and formation of ferricenium tetrahaloferrate salts.     

Far-Red Dibenzo[a,j]Perylene-8,16-Dione Dyes as Fluorescent Enzyme Substrates and Tags for Biomolecules

The synthesis of fluorescent 2,10-derivatives of the title chromophore are described. The substituents contain amino-reactive N-hydroxysuccinimde ester and thiol-reactive iodoacetamide groups for attachment to biomolecules. A phosphate derivative was also prepared as an enzyme substrate.     

Comparison of rigid and flexible simple point charge water models at supercritical conditions

This study investigates the differences between the predictions of various properties of rigid and flexible simple point charge water models at supercritical conditions. Molecular dynamics simulations were conducted for supercritical water in a temperature range of 773–1073 K and densities in the range 115–659 kg/m³. We present thermodynamic data, pair correlation functions, self-diffusivity, power spectra, dielectric constants, and variaous measures of hydrogen bonding at different state conditions. The flexible water model performs better in predicting the pressures along the supercritical isotherms simulated. Agreement between experimental and calculated dielectric constants is superior for the flexible water model, particularly at high densities. The flexible model exhibits a greater degree of hydrogen bonding and more persistent hydrogen bonds than does the rigid model. The structural features of supercritical water at high densities are identical for the two water models. At low densities, however, the flexible potential exhibits pair correlation functions with enhanced peaks. Inclusion of flexibility in the potential model does not result in a significant shift in the position of the rotational/librational peak in the power spectrum. The self-diffusivities obtained from the simulations are within the accuracy of the experimental values for both the rigid and flexible models. On balance the inclusion of flexibility improves agreement with the properties of real supercritical water while incurring little or no additional computational burden. © 1996 by John Wiley & Sons, Inc.     

SSD‐enhanced uncoded space‐time labeling diversity

Space‐time labeling diversity (STLD) has been shown to be an efficient technique for improving the bit error rate (BER) performance of an uncoded space‐time coded modulation system. In this paper, signal space diversity (SSD) is incorporated into the uncoded STLD system to further enhance the system BER performance. A tight closed‐form union bound on the BER of the proposed system is derived and is used to optimize the rotation angle of the SSD scheme. Simulation results are used to confirm the theoretical bound derived for the system. The results also show performance gains of approximately 2.0 dB at a BER of 10^?6 and 1.6 dB at a BER 10^?4 from incorporating SSD into the uncoded STLD system using 16QAM and 64QAM, respectively. Furthermore, a low complexity detection scheme based on orthogonal projection is formulated for the proposed scheme and, in comparison with the optimal maximum‐likelihood detector, is shown to result in a 56% and 95% reduction in computation complexity for the 16QAM and 64QAM versions of the proposed system, respectively.     

Symbol error rate calculation and data pre‐distortion for 16‐QAM transmission over nonlinear memoryless satellite channels

This paper presents a simplified mathematical approach to evaluate the performance of any given circular constellation of 16‐level quadrature amplitude modulation (16‐QAM) in terms of symbol error rate (SER). Following this approach, with the aim to work with memoryless nonlinear satellite channels, a model is derived as a generalized form for both linear and nonlinear channels in the presence of down link additive white Gaussian noise (AWGN). The analysis provides means to calculate the optimal ring ratio (RR) and phase difference (PD) for several possible candidates of 16‐QAM circular constellations. The effects of RR and PD on the SER performance are investigated in the analysis. To overcome the nonlinear distortion, data pre‐distortion is taken into account in the study. The paper gives a general procedure for data pre‐distortion implementation for all circular 16‐QAM constellations. The analytical formulation has been extended for total degradation (TD) performance measure as a function of input back‐off (IBO) of the nonlinear amplifier. A SER performance‐comparison between different constellations for 16‐QAM systems has also been presented in this paper. The analytical results are validated by simulation. Copyright © 2006 John Wiley & Sons, Ltd.     

Resource efficient network design and traffic grooming strategy with guaranteed survivability

In WDM networks, path protection has emerged as a widely accepted technique for providing guaranteed survivability of network traffic. However, it requires allocating resources for backup lightpaths, which remain idle under normal fault-free conditions. In this paper, we introduce a new design strategy for survivable network design, which guarantees survivability of all ongoing connections that requires significantly fewer network resources than protection based techniques. In survivable routing, the goal is to find a Route and Wavelength Assignment (RWA) such that the logical topology remains connected for all single link failures. However, even if the logical topology remains connected after any single link fault, it may not have sufficient capacity to support all the requests for data communication, for all single fault scenarios. To address this deficiency, we have proposed two independent but related problem formulations. To handle our first formulation, we have presented an Integer Linear Program (ILP) that augments the concept of survivable routing by allowing rerouting of sub-wavelength traffic carried on each lightpath and finding an RWA that maximizes the amount of traffic that can be supported by the network in the presence of any single link failure. To handle our second formulation, we have proposed a new design approach that integrates the topology design and the RWA in such a way that the resulting logical topology is able to handle the entire set of traffic requests after any single link failure. For the second problem, we have first presented an ILP formulation for optimally designing a survivable logical topology, and then proposed a heuristic for larger networks. Experimental results demonstrate that this new approach is able to provide guaranteed bandwidth, and is much more efficient in terms of resource utilization, compared to both dedicated and shared path protection schemes.     

Performance analysis of M‐APSK generalised spatial modulation with constellation reassignment

Generalised spatial modulation (GSM) is a recently developed multiple‐input multiple‐output (MIMO) technique aimed at improving data rates over conventional spatial modulation (SM) systems. However, for identical antenna array size and configurations (AASC), the bit error rate (BER) of GSM systems in comparison with SM systems is degraded. Recently, a GSM system with constellation reassignment (GSM‐CR) was proposed in order to improve the BER of traditional GSM systems. However, this study focused on M‐ary quadrature amplitude modulation (M‐QAM) schemes. The focus of this paper is the application of a circular constellations scheme, in particular, amplitude phase shift keying (APSK) modulation, to GSM and GSM‐CR systems. An analytical bound for the average BER of the proposed M‐APSK GSM and M‐APSK GSM‐CR systems over fading channels is derived. The accuracy of this bound is verified using Monte Carlo simulation results. A 4 × 4 16‐APSK GSM‐CR system achieves a gain of 2.5 dB at BER of 10^?5 over the traditional 16‐APSK GSM system with similar AASC. Similarly, a 6 × 4 32‐APSK GSM‐CR system achieves a gain of 2 dB at BER of 10^?5 over equivalent 32‐APSK GSM system.     

Systematic search for spontaneous neutral to ionic and ionic to neutral transitions in organometallic materials based on minimally alkylated ferrocenes and classical polycyanide electron acceptors

Methyl-, ethyl- and n-butyl ferrocene (I–III) form dark colored charge transfer complexes with TCNE both in solution and by trituration of the solid donor and acceptor. Their Mössbauer spectra suggest only minor reduction of the TCNE acceptor. On the other hand, 1,1-dimethylferrocene (IV) forms a ferricenium complex with TCNE of 12 stoichiometry whose structure is likely similar to that determined for [IV][TCNQ]₂. The new 12 ferricenium-TCNE phase undergoes a novel, spontaneous, irreversible solid-state transformation back to a mixture of a low spin Fe^II ferrocene species and a high spin Fe^II complex over a period of weeks at ambient temperature. In preliminary studies, irradiation of samples of these materials with white light (including near infrared wavelengths) suggests significant photochemical activity of the type and vice versa in the solid state. This is observable in Mössbauer spectra at 77 K. In the absence of irradiation with tungsten-halogen white light sources, however, the photo product is not permanently trapped at this temperature.     

A Novel Synthesis of 1-Aryl-9-alkyl-2, 3, 3a, 4, 9, 9a-hexahydro-1H-pyrrolo[2, 3-b] quinoxalines by lithium aluminium hydride reduction of N-phenyl-1-benzimidazolyl-succinimides

The N-substituted 1-benzimidazolyl-succinimides 6a – v (Scheme 1, Table 1 and 2) have been prepared by the reaction of benzimidazole and its derivatives with maleimides. Reduction of the N-cyclohexyl and N-cyclo-octyl substituted 1-benzimidazolyl-succinimides 6i – k with lithium aluminium hydride gives the normally expected substituted (N-alkyl-3-pyrrolidinyl)benzimidazoles 14i – k . However by LiAlH₄-reduction of the N-phenyl substituted 1-benzimidazolylsuccinimides 6a – h mainly the 1-aryl-9-alkyl-2, 3, 3a, 4, 9, 9a-hexahydro-1H-pyrrolo[2, 3-b]quinoxalines 7a – h are obtained. The mechanism of this unusual reduction has been elucidated.     

Characterization of a Series of Far Red Absorbing Perylene Diones: A New Class of Fluorescent Probes for Biological Applications

The far red region of the spectrum is increasingly being utilised in many applications in the biosciences. However, apart from the cyanine group of dyes, there are relatively few far red fluorescent probes available which are of practical use. We have synthesised and characterised a new class of far red fluorescent probes based on the perylene dione chromophore. The 2,10 di-substituted perylene diones possess broad absorption spectra (>90 nm bandwidths), large Stokes shifts (>60 nm) and quantum yields of up to 0.5 with a maximum absorption at 610–640 nm in organic solvents or in solutions of non-ionic detergents. A number of derivatives have been synthesised that can be used as membrane probes, as chromogenic substrates for alkaline phosphatase, and for the labelling of macromolecules such as proteins and DNA. These novel far red fluorophores have potential applications in diagnostic and research applications.