Preparation of metal-TCNQ charge-transfer complexes on conducting and insulating surfaces by photocrystallization

A generic method for the synthesis of metal-7,7,8,8-tetracyanoquinodimethane (TCNQ) charge-transfer complexes on both conducting and nonconducting substrates is achieved by photoexcitation of TCNQ in acetonitrile in the presence of a sacrificial electron donor and the relevant metal cation. The photochemical reaction leads to reduction of TCNQ to the TCNQ- monoanion. In the presence of Mx+(MeCN), reaction with TCNQ-(MeCN) leads to deposition of Mx+[TCNQ]x crystals onto a solid substrate with morphologies that are dependent on the metal cation. Thus, CuTCNQ phase I photocrystallizes as uniform microrods, KTCNQ as microrods with a random size distribution, AgTCNQ as very long nanowires up to 30 μm in length and with diameters of less than 180 nm, and Co[TCNQ]2(H2O)2 as nanorods and wires. The described charge-transfer complexes have been characterized by optical and scanning electron microscopy and IR and Raman spectroscopy. The CuTCNQ and AgTCNQ complexes are of particular interest for use in memory storage and switching devices. In principle, this simple technique can be employed to generate all classes of metal−TCNQ complexes and opens up the possibility to pattern them in a controlled manner on any type of substrate.

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.

Extensive charge-discharge cycling of lithium metal electrodes achieved using ionic liquid electrolytes

The effect of extended cycling on lithium metal electrodes has been investigated in an ionic liquid electrolyte. Cycling studies were conducted on lithium metal electrodes in a symmetrical Li|electrolyte|Li coin cell configuration for 5000 charge–discharge cycles at a current density of 0.1 mA cm− 2. The voltage–time plots show evidence of some unstable behavior which is attributed to surface reorganization. No evidence for lithium dendrite induced short circuiting was observed. SEM imaging showed morphology changes had occurred but no evidence of needle-like dendrite based growth was found after 5000 charge–discharge cycles. This study suggests that ionic liquid electrolytes can enable next generation battery technologies such as rechargeable lithium-air, in which a safe, reversible lithium electrode is a crucial component.

Probing the effect of charge transfer enhancement in off resonance mode SERS via conjugation of the probe dye between silver nanoparticles and metal substrates

The charge transfer-mediated surface enhanced Raman scattering (SERS) of crystal violet (CV) molecules that were chemically conjugated between partially polarized silver nanoparticles and optically smooth gold and silver substrates has been studied under off-resonant conditions. Tyrosine molecules were used as a reducing agent to convert silver ions into silver nanoparticles where oxidised tyrosine caps the silver nanoparticle surface with its semiquinone group. This binding through the quinone group facilitates charge transfer and results in partially oxidised silver. This establishes a chemical link between the silver nanoparticles and the CV molecules, where the positively charged central carbon of CV molecules can bind to the terminal carboxylate anion of the oxidised tyrosine molecules. After drop casting Ag nanoparticles bound with CV molecules it was found that the free terminal amine groups tend to bind with the underlying substrates. Significantly, only those CV molecules that were chemically conjugated between the partially polarised silver nanoparticles and the underlying gold or silver substrates were found to show SERS under off-resonant conditions. The importance of partial charge transfer at the nanoparticle/capping agent interface and the resultant conjugation of CV molecules to off resonant SERS effects was confirmed by using gold nanoparticles prepared in a similar manner. In this case the capping agent binds to the nanoparticle through the amine group which does not facilitate charge transfer from the gold nanoparticle and under these conditions SERS enhancement in the sandwich configuration was not observed.

Lateral charge propagation effects during the galvanic replacement of electrodeposited MTCNQ (M= Cu, Ag) microstructures with gold and its influence on catalysed electron transfer reactions

The galvanic replacement of isolated electrodeposited semiconducting CuTCNQ microstructures on a glassy carbon (GC) substrate with gold is investigated. It is found that anisotropic metal nanoparticles are formed which are not solely confined to the redox active sites on the semiconducting materials but are also observed on the GC substrate which occurs via a lateral charge propagation mechanism. We also demonstrate that this galvanic replacement approach can be used for the formation of isolated AgTCNQ/Au microwire composites which occurs via an analogous mechanism. The resultant MTCNQ/Au (M = Cu, Ag) composite materials are characterized by Raman, spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and investigated for their catalytic properties for the reduction of ferricyanide ions with thiosulphate ions in aqueous solution. Significantly it is demonstrated that gold loading, nanoparticle shape and in particular the MTCNQ–Au interface are important factors that influence the reaction rate. It is shown that there is a synergistic effect at the CuTCNQ/Au composite when compared to AgTCNQ/Au at similar gold loadings.

Public acceptance towards congestion charge : a case study of Brisbane

This paper investigates public acceptance towards congestion charge in Australia by taking Brisbane as a case study. Public acceptance to congestion charge has often been investigated in the literature. However, few were in the context of an Australian city. This paper fills the gap. A face-to-face survey was conducted to solicit public opinions on the congestion charge, should a congestion charge scheme be implemented in the Brisbane City area. The survey data were analysed to pinpoint important factors relevant to people’s attitudes towards congestion charge and to measure their relationships. Main findings from our analysis are: (1) the residents’ attitudes towards congestion charge differ by genders and by user groups of transport modes; (2) for each of the three groups (i.e., the auto users, the transit riders, and the whole participants), a positive and stable correlation was found between a participant’s attitude towards congestion charge and the effectiveness of congestion charge on reducing traffic congestion. A negative and stable correlation was also found for all three groups between a participant’s attitude towards congestion charge and congestion charge’s negative impact on the attractiveness of working in the city; (3) the auto users tended to be more sceptical about the service capacity of existing transit systems in coping with extra passengers induced by the implementation of congestion charge; and (4) for people with high income, introducing the congestion charge may have no impact on their travelling to the city.

A variable diffusivity model for the drying of spherical food particulates

An investigation of the drying of spherical food particles was performed, using peas as the model material. In the development of a mathematical model for drying curves, moisture diffusion was modelled using Fick’s second law for mass transfer. The resulting partial differential equation was solved using a forward-time central-space finite difference approximation, with the assumption of variable effective diffusivity. In order to test the model, experimental data was collected for the drying of green peas in a fluidised bed at three drying temperatures. Through fitting three equation types for effective diffusivity to the data, it was found that a linear equation form, in which diffusivity increased with decreasing moisture content, was most appropriate. The final model accurately described the drying curves of the three experimental temperatures, with an R2 value greater than 98.6% for all temperatures.

Ureaplasma parvum undergoes selection in utero resulting in genetically diverse isolates colonising the chorioamnion of fetal sheep

Ureaplasmas are the microorganisms most frequently isolated from the amniotic fluid of pregnant women and can cause chronic intrauterine infections. These tiny bacteria are thought to undergo rapid evolution and exhibit a hypermutatable phenotype; however, little is known about how ureaplasmas respond to selective pressures in utero. Using an ovine model of chronic intra-amniotic infection, we investigated if exposure of ureaplasmas to sub-inhibitory concentrations of erythromycin could induce phenotypic or genetic indicators of macrolide resistance. At 55 days gestation, 12 pregnant ewes received an intra-amniotic injection of a non-clonal, clinical U. parvum strain, followed by: (i) erythromycin treatment (IM, 30 mg/kg/day, n=6); or (ii) saline (IM, n=6) at 100 days gestation. Fetuses were then delivered surgically at 125 days gestation. Despite injecting the same inoculum into all ewes, significant differences between amniotic fluid and chorioamnion ureaplasmas were detected following chronic intra-amniotic infection. Numerous polymorphisms were observed in domain V of the 23S rRNA gene of ureaplasmas isolated from the chorioamnion (but not the amniotic fluid), resulting in a mosaic-like sequence. Chorioamnion isolates also harboured the macrolide resistance genes erm(B) and msr(D) and were associated with variable roxithromycin minimum inhibitory concentrations. Remarkably, this variability occurred independently of exposure of ureaplasmas to erythromycin, suggesting that low-level erythromycin exposure does not induce ureaplasmal macrolide resistance in utero. Rather, the significant differences observed between amniotic fluid and chorioamnion ureaplasmas suggest that different anatomical sites may select for ureaplasma sub-types within non-clonal, clinical strains. This may have implications for the treatment of intrauterine ureaplasma infections.

A new procedure for using envelope analysis for rolling element bearing diagnostics in variable operating conditions

In the field of rolling element bearing diagnostics envelope analysis, and in particular the squared envelope spectrum, have gained in the last years a leading role among the different digital signal processing techniques. The original constraint of constant operating speed has been relaxed thanks to the combination of this technique with the computed order tracking, able to resample signals at constant angular increments. In this way, the field of application of squared envelope spectrum has been extended to cases in which small speed fluctuations occur, maintaining the effectiveness and efficiency that characterize this successful technique. However, the constraint on speed has to be removed completely, making envelope analysis suitable also for speed and load transients, to implement an algorithm valid for all the industrial application. In fact, in many applications, the coincidence of high bearing loads, and therefore high diagnostic capability, with acceleration-deceleration phases represents a further incentive in this direction. This paper is aimed at providing and testing a procedure for the application of envelope analysis to speed transients. The effect of load variation on the proposed technique will be also qualitatively addressed.

Application of cepstrum pre-whitening for the diagnosis of bearing faults under variable speed conditions

Diagnostics of rolling element bearings involves a combination of different techniques of signal enhancing and analysis. The most common procedure presents a first step of order tracking and synchronous averaging, able to remove the undesired components, synchronous with the shaft harmonics, from the signal, and a final step of envelope analysis to obtain the squared envelope spectrum. This indicator has been studied thoroughly, and statistically based criteria have been obtained, in order to identify damaged bearings. The statistical thresholds are valid only if all the deterministic components in the signal have been removed. Unfortunately, in various industrial applications, characterized by heterogeneous vibration sources, the first step of synchronous averaging is not sufficient to eliminate completely the deterministic components and an additional step of pre-whitening is needed before the envelope analysis. Different techniques have been proposed in the past with this aim: The most widely spread are linear prediction filters and spectral kurtosis. Recently, a new technique for pre-whitening has been proposed, based on cepstral analysis: the so-called cepstrum pre-whitening. Owing to its low computational requirements and its simplicity, it seems a good candidate to perform the intermediate pre-whitening step in an automatic damage recognition algorithm. In this paper, the effectiveness of the new technique will be tested on the data measured on a full-scale industrial bearing test-rig, able to reproduce the harsh conditions of operation. A benchmark comparison with the traditional pre-whitening techniques will be made, as a final step for the verification of the potentiality of the cepstrum pre-whitening.

Fault symptoms of rolling element bearings under variable operating conditions - a multi domain analysis

Diagnostics of rolling element bearings have been traditionally developed for constant operating conditions, and sophisticated techniques, like Spectral Kurtosis or Envelope Analysis, have proven their effectiveness by means of experimental tests, mainly conducted in small-scale laboratory test-rigs. Algorithms have been developed for the digital signal processing of data collected at constant speed and bearing load, with a few exceptions, allowing only small fluctuations of these quantities. Owing to the spreading of condition based maintenance in many industrial fields, in the last years a need for more flexible algorithms emerged, asking for compatibility with highly variable operating conditions, such as acceleration/deceleration transients. This paper analyzes the problems related with significant speed and load variability, discussing in detail the effect that they have on bearing damage symptoms, and propose solutions to adapt existing algorithms to cope with this new challenge. In particular, the paper will i) discuss the implication of variable speed on the applicability of diagnostic techniques, ii) address quantitatively the effects of load on the characteristic frequencies of damaged bearings and iii) finally present a new approach for bearing diagnostics in variable conditions, based on envelope analysis. The research is based on experimental data obtained by using artificially damaged bearings installed on a full scale test-rig, equipped with actual train traction system and reproducing the operation on a real track, including all the environmental noise, owing to track irregularity and electrical disturbances of such a harsh application.

Order tracking for discrete-random separation in variable speed conditions

The transmission path from the excitation to the measured vibration on the surface of a mechanical system introduces a distortion both in amplitude and in phase. Moreover, in variable speed conditions, the amplification/attenuation and the phase shift, due to the transfer function of the mechanical system, varies in time. This phenomenon reduces the effectiveness of the traditionally tachometer based order tracking, compromising the results of a discrete-random separation performed by a synchronous averaging. In this paper, for the first time, the extent of the distortion is identified both in the time domain and in the order spectrum of the signal, highlighting the consequences for the diagnostics of rotating machinery. A particular focus is given to gears, providing some indications on how to take advantage of the quantification of the disturbance to better tune the techniques developed for the compensation of the distortion. The full theoretical analysis is presented and the results are applied to an experimental case.

The IL-6 response to Chlamydia from primary reproductive epithelial cells is highly variable and may be involved in differential susceptibility to the immunopathological consequences of chlamydial infection

Background Chlamydia trachomatis infection results in reproductive damage in some women. The process and factors involved in this immunopathology are not well understood. This study aimed to investigate the role of primary human cellular responses to chlamydial stress response proteases and chlamydial infection to further identify the immune processes involved in serious disease sequelae. Results Laboratory cell cultures and primary human reproductive epithelial cultures produced IL-6 in response to chlamydial stress response proteases (CtHtrA and CtTsp), UV inactivated Chlamydia, and live Chlamydia. The magnitude of the IL-6 response varied considerably (up to 1000 pg ml-1) across different primary human reproductive cultures. Thus different levels of IL-6 production by reproductive epithelia may be a determinant in disease outcome. Interestingly, co-culture models with either THP-1 cells or autologous primary human PBMC generally resulted in increased levels of IL-6, except in the case of live Chlamydia where the level of IL-6 was decreased compared to the epithelial cell culture only, suggesting this pathway may be able to be modulated by live Chlamydia. PBMC responses to the stress response proteases (CtTsp and CtHtrA) did not significantly vary for the different participant cohorts. Therefore, these proteases may possess conserved innate PAMPs. MAP kinases appeared to be involved in this IL-6 induction from human cells. Finally, we also demonstrated that IL-6 was induced by these proteins and Chlamydia from mouse primary reproductive cell cultures (BALB/C mice) and mouse laboratory cell models. Conclusions We have demonstrated that IL-6 may be a key factor for the chlamydial disease outcome in humans, given that primary human reproductive epithelial cell culture showed considerable variation in IL-6 response to Chlamydia or chlamydial proteins, and that the presence of live Chlamydia (but not UV killed) during co-culture resulted in a reduced IL-6 response suggesting this response may be moderated by the presence of the organism.

Formation and Fragmentation of Unsaturated Fatty Acid M-2H+Na (-) Ions: Stabilized Carbanions for Charge-Directed Fragmentation

Fatty acids are long-chain carboxylic acids that readily produce \[M - H](-) ions upon negative ion electrospray ionization (ESI) and cationic complexes with alkali, alkaline earth, and transition metals in positive ion ESI. In contrast, only one anionic monomeric fatty acid-metal ion complex has been reported in the literature, namely \[M - 2H + (FeCl)-Cl-II](-). In this manuscript, we present two methods to form anionic unsaturated fatty acid-sodium ion complexes (i.e., \[M - 2H + Na](-)). We find that these ions may be generated efficiently by two distinct methods: (1) negative ion ESI of a methanolic solution containing the fatty acid and sodium fluoride forming an \[M - H + NaF](-) ion. Subsequent collision-induced dissociation (CID) results in the desired \[M - 2H + Na](-) ion via the neutral loss of HF. (2) Direct formation of the \[M - 2H + Na](-) ion by negative ion ESI of a methanolic solution containing the fatty acid and sodium hydroxide or bicarbonate. In addition to deprotonation of the carboxylic acid moiety, formation of \[M - 2H + Na](-) ions requires the removal of a proton from the fatty acid acyl chain. We propose that this deprotonation occurs at the bis-allylic position(s) of polyunsaturated fatty acids resulting in the formation of a resonance-stabilized carbanion. This proposal is supported by ab initio calculations, which reveal that removal of a proton from the bis-allylic position, followed by neutral loss of HX (where X = F- and -OH), is the lowest energy dissociation pathway.