Iron(II) spin-transition complexes with dendritic ligands, part II

The dendritic triazole-based complexes \[Fe(G1-BOC)3](triflate) 2·xH2O (1; G1-BOC = tert-butyl {3-\[3-(3-tert- butoxycarbonylaminopropyl)-5-(\[1,2,4]triazol-4-ylcarbamoyl)-phenyl]propyl} carbamate, triflate = CF3SO3-), \[Fe(G1-BOC) 3]-(tosylate)2·xH2O(2;tosylate = p-CH3PhSO3-),\[Fe(G1-DPBE)3]-(triflate) 2·xH2O {3; G1-DPBE = 3,5-bis(3,5- didodecaoxybenzyloxy)-N-\[1,2,4]triazol-4-ylbenzamide}, \[Fe(G1-DPBE) 3]-(tosylate)2·xH2O (4) and \[Fe(G1-DPBE)3](BF4)2·xH2O (5) were designed and synthesized. Magnetic and thermal properties of these novel complexes were characterized by magnetic susceptibility measurements, 57Fe Mössbauer spectroscopy and thermogravimetric analysis or differential scanning calorimetry, respectively. All dendritic complexes under study show different spin-transition behaviour with respect to the nature of different dendritic ligands and counteranions. Complexes 1 and 2 have pronounced effects of a spin-state change during the first heating process and gradual spintransition properties for further temperature treatments, whereas 3 and 4 exhibited a very sharp spin-state change in the first heating procedures. Complex 5 showed a gradual spin-transition curve. In this paper, we report how the magnetic properties of these complexes are correlated with noncoordinated water molecules and their effects on spin states.

Changes in environmentally sensitive productivity and technological modernization in China's iron and steel industry in the 1990s

Technological modernization is widely believed to contribute positively both to economic development and to environmental and resource conservation, through improvements in productivity and strengthening of business competitiveness. However, this may not always be true, particularly in the short term, as it requires substantial investments and may impose financial burdens on firms undertaking such investments. This study empirically examines the effects of technological modernization in China's iron and steel industry in the 1990s on conventional economic productivity (CEP) and environmentally sensitive productivities (ESPs). We employ a directional distance function that can handle multiple inputs and outputs to compute relative production efficiencies. We apply these models to the data covering 27 iron and steel firms in China between 1990 and 1999-a period when the Chinese iron and steel industry modernized rapidly. We find that ESPs have continuously improved, even in the period when the CEP declined.

Ultrathin hematite films deposited layer-by-layer on TiO2 underlayer for efficient water splitting under visible light

Ultrathin hematite (α-Fe2O3) film deposited on a TiO2 underlayer as a photoanode for photoelectrochemical water splitting was described. The TiO2 underlayer was coated on conductive fluorine-doped tin oxide (FTO) glass by spin coating. The hematite films were formed layer-by-layer by repeating the separated two-phase hydrolysis-solvothermal reaction of iron(III) acetylacetonate and aqueous ammonia. A photocurrent density of 0.683 mA cm−2 at +1.5 V vs. RHE (reversible hydrogen electrode) was obtained under visible light (>420 nm, 100 mW cm−2) illumination. The TiO2 underlayer plays an important role in the formation of hematite film, acting as an intermediary to alleviate the dead layer effect and as a support of large surface areas to coat greater amounts of Fe2O3. The as-prepared photoanodes are notably stable and highly efficient for photoelectrochemical water splitting under visible light. This study provides a facile synthesis process for the controlled production of highly active ultrathin hematite film and a simple route for photocurrent enhancement using several photoanodes in tandem.

The use of correspondence analysis to compare major and trace elements for provenance studies of iron-age pottery from the Mngeni river area, South Africa

Provenance studies of iron-age pottery specimens originating from the Mngeni river area in South Africa was carried out by applying XRF spectrometry. A total of sixteen major and trace elements were analysed in a batch of 107 potsherds, excavated from four different archaeological sites in the aforementioned area. A multivariate statistical programme Correspondence Analysis was used in this study to obtain the relevant clustering patterns according to the similarity of the elemental distributions. Differences and similarities in the clusters obtained for the majors and trace elements are discussed.

A study, by fire-assay and ICP-MS, of the distribution of rhodium, platinum, and gold in iron-age pottery

Forty-six archaeological specimens were treated by fire-assay and subsequently analysed by ICP-MS for selected precious metals: Ph, Pt and Au. The investigation was prompted by the possibility that archaeological samples could serve as "indicators" of the precious metal composition of the clays from the excavated sites. Therefore, the experimentally obtained concentrations were carefully studied to determine if there were anomalous levels of these precious metals in the deposits from which the specimens originated. Furthermore, the analytical data were used to establish if it was feasible to distinguish ancient potsherds based on precious metal concentrations, for employment as a basis in provenance studies.

PSMA-targeting iron oxide magnetic nanoparticles enhance MRI of preclinical prostate cancer

Aim Evaluate potential of newly-developed, biocompatible iron oxide magnetic nanoparticles (MNPs) conjugated with J591, an antibody to an extracellular epitope of prostate specific membrane antigen (PSMA), to enhance MRI of prostate cancer (PCa). Materials & Methods Specific binding to PSMA by J591-MNP was investigated in vitro. MRI studies were performed on orthotopic tumor-bearing NOD.SCID mice 2h and 24hr after intravenous injection of J591-MNPs, or non-targeting MNPs. Results and Conclusions In vitro, MNPs did not affect PCa cell viability, and conjugation to J591 did not compromise antibody specificity and enhanced cellular iron uptake. In vivo, PSMA-targeting MNPs increased MR contrast of tumors, but not by non-targeting MNPs. This provides proof-of-concept that PSMA-targeting MNPs have potential to enhance MR detection/localization of PCa.,

Enhancing MRI of prostate cancer using PSMA-targeting iron oxide magnetic nanoparticles

Introduction Novel imaging techniques for prostate cancer (PCa) are required to improve staging and real-time assessment of therapeutic response. We performed preclinical evaluation of newly-developed, biocompatible magnetic nanoparticles (MNPs) conjugated with J591, an antibody specific for prostate specific membrane antigen (PSMA), to enhance magnetic resonance imaging (MRI) of PCa. PSMA is expressed on ∼90% of PCa, including those that are castrate-resistant, rendering it as a rational target for PCa imaging. Materials and Methods The specificity of J591 for PSMA was confirmed by flow cytometric analysis of several PCa cell lines of known PSMA status. MNPs were prepared, engineered to the appropriate size, labeled with DiR fluorophore, and their toxicity to a panel of PC cells was assessed by in vitro Alamar Blue assay. Immunohistochemistry, fluorescence microscopy and Prussian Blue staining (iron uptake) were used to evaluate PSMA specificity of J591-MNP conjugates. In vivo MRI studies (16.4T MRI system) were performed using live immunodeficient mice bearing orthotopic LNCaP xenografts and injected intravenously with J591-MNPs or MNPs alone. Results MNPs were non-toxic to PCa cells. J591-MNP conjugates showed no compromise in specificity of binding to PSMA+ cells and showed enhanced iron uptake compared with MNPs alone. In vivo, tumour targeting (significant MR image contrast) was evident in mice injected with J591-MNPs, but not MNPs alone. Resected tumours from targeted mice had an accumulation of MNPs, not seen in normal control prostate. Conclusions Application of PSMA-targeting MNPs into conventional MRI has potential to enhance PCa detection and localization in real-time, improving patient management.

Follow the lighthouse route in Nova Scotia, Canada

Within half an hour of leaving Halifax Airport I managed to get myself lost. I noticed an exit sign for St Margaret’s Bay and, despite written instructions to the contrary, it sounded like the right way to go. But I was on the Lighthouse Route and on my way back to Halifax...

Transit route occupancy load factor and passenger average travel time for quality of service assessment

This paper investigates quality of service (QoS) and resource productivity implications of transit route passenger loading and travel time. It highlights the value of occupancy load factor as a direct passenger comfort QoS measure. Automatic Fare Collection data for a premium radial bus route in Brisbane, Australia, is used to investigate time series correlation between occupancy load factor and passenger average travel time. Correlation is strong across the entire span of service in both directions. Passengers tend to be making longer, peak direction commuter trips under significantly less comfortable conditions than off-peak. The Transit Capacity and Quality of Service Manual uses segment based load factor as a measure of onboard loading comfort QoS. This paper provides additional insight into QoS by relating the two route based dimensions of occupancy load factor and passenger average travel time together in a two dimensional format, both from the passenger’s and operator’s perspectives. Future research will apply Value of Time to QoS measurement, reflecting perceived passenger comfort through crowding and average time spent onboard. This would also assist in transit service quality econometric modeling. The methodology can be readily applied in a practical setting where AFC data for fixed scheduled routes is available. The study outcomes also provide valuable research and development directions.

Transit route occupancy load factor and passenger average travel time for quality of service assessment

This presentation investigates quality of service (QoS) and resource productivity implications of transit route passenger loading and travel time. It highlights the value of occupancy load factor as a direct passenger comfort QoS measure. Automatic Fare Collection data for a premium radial bus route in Brisbane, Australia, is used to investigate time series correlation between occupancy load factor and passenger average travel time. Correlation is strong across the entire span of service in both directions. Passengers tend to be making longer, peak direction commuter trips under significantly less comfortable conditions than off-peak. The Transit Capacity and Quality of Service Manual uses segment based load factor as a measure of onboard loading comfort QoS. This paper provides additional insight into QoS by relating the two route based dimensions of occupancy load factor and passenger average travel time together in a two dimensional format, both from the passenger’s and operator’s perspectives. Future research will apply Value of Time to QoS measurement, reflecting perceived passenger comfort through crowding and average time spent onboard. This would also assist in transit service quality econometric modeling. The methodology can be readily applied in a practical setting where AFC data for fixed scheduled routes is available. The study outcomes also provide valuable research and development directions.

Stochastic analysis of transit route segments' passenger load variation for capacity and quality of service assessment

This paper investigates stochastic analysis of transit segment hourly passenger load factor variation for transit capacity and quality of service (QoS) analysis using Automatic Fare Collection data for a premium radial bus route in Brisbane, Australia. It compares stochastic analysis to traditional peak hour factor (PHF) analysis to gain further insight into variability of transit route segments’ passenger loading during a study hour. It demonstrates that hourly design load factor is a useful method of modeling a route segment’s capacity and QoS time history across the study weekday. This analysis method is readily adaptable to different passenger load standards by adjusting design percentile, reflecting either a more relaxed or more stringent condition. This paper also considers hourly coefficient of variation of load factor as a capacity and QoS assessment measure, in particular through its relationships with hourly average and design load factors. Smaller value reflects uniform passenger loading, which is generally indicative of well dispersed passenger boarding demands and good schedule maintenance. Conversely, higher value may be indicative of pulsed or uneven passenger boarding demands, poor schedule maintenance, and/or bus bunching. An assessment table based on hourly coefficient of variation of load factor is developed and applied to this case study. Inferences are drawn for a selection of study hours across the weekday studied.

Stochastic analysis of transit route segments' passenger load variation for capacity & quality of service assessment

This study uses weekday Automatic Fare Collection (AFC) data on a premium bus line in Brisbane, Australia •Stochastic analysis is compared to peak hour factor (PHF) analysis for insight into passenger loading variability •Hourly design load factor (e.g. 88th percentile) is found to be a useful method of modeling a segment’s passenger demand time-history across a study weekday, for capacity and QoS assessment •Hourly coefficient of variation of load factor is found to be a useful QoS and operational assessment measure, particularly through its relationship with hourly average load factor, and with design load factor •An assessment table based on hourly coefficient of variation of load factor is developed from the case study

Cathodic corrosion of Cu substrates as a route to nanostructured Cu/M (M = Ag, Au, Pd) surfaces

The electrochemical formation of nanostructured materials is generally achieved by reduction of a metal salt onto a substrate that does not influence the composition of the deposit. In this work we report that Ag, Au and Pd electrodeposited onto Cu under conditions where galvanic replacement is not viable and hydrogen gas is evolved results in the formation of nanostructured surfaces that unexpectedly incorporate a high concentration of Cu in the final material. Under cathodic polarization conditions the electrodissolution/corrosion of Cu occurs which provides a source of ionic copper that is reduced at the surface-electrolyte interface. The nanostructured Cu/M (M = Ag, Au and Pd) surfaces are investigated for their catalytic activity for the reduction of 4 nitrophenol by NaBH4 where Cu/Ag was found to be extremely active. This work indicates that a substrate electrode can be utilized in an interesting manner t make bimetallic nanostructures with enhanced catalytic activity.

Equilibrium and column studies of iron exchange with strong acid cation resin

The exchange of iron species from iron (III) chloride solutions with a strong acid cation resin has been investigated in relation to a variety of water and wastewater applications. A detailed equilibrium isotherm analysis was conducted wherein models such as Langmuir Vageler, Competitive Langmuir, Freundlich, Temkin, Dubinin Astakhov, Sips and Brouers-Sotolongo were applied to the experimental data. An important conclusion was that both the bottle-point method and solution normality used to generate the ion exchange equilibrium information influenced which sorption model fitted the isotherm profiles optimally. Invariably, the calculated value for the maximum loading of iron on strong acid cation resin was substantially higher than the value of 47.1 g/kg of resin which would occur if one Fe3+ ion exchanged for three “H+” sites on the resin surface. Consequently, it was suggested that above pH 1, various iron complexes sorbed to the resin in a manner which required less than 3 sites per iron moiety. Column trials suggested that the iron loading was 86.6 g/kg of resin when 1342 mg/L Fe (III) ions in water were flowed at 31.7 bed volumes per hour. Regeneration with 5 to 10 % HCl solutions reclaimed approximately 90 % of exchange sites.