Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Two-dimensional simulation of nanoassembly precursor species in Ar+H2+C2H2 reactive plasmas

The results of two-dimensional fluid simulation of number densities and fluxes of the main building blocks and surface preparation species involved in nanoassembly of carbon-based nanopatterns in Ar+H2+C2H2 reactive plasmas are reported. It is shown that the process parameters and non-uniformity of surface fluxes of each particular species may affect the targeted nanopattern quality. The results can be used to improve predictability of plasma-aided nanofabrication processes and optimize the parameters of plasma nanotools.KGaA, Weinheim.

Decomposition of toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008

This study analyzes toxic chemical substance management in three U.S. manufacturing sectors from 1991 to 2008. Decomposition analysis applying the logarithmic mean Divisia index is used to analyze changes in toxic chemical substance emissions by the following five factors: cleaner production, end-of-pipe treatment, transfer for further management, mixing of intermediate materials, and production scale. Based on our results, the chemical manufacturing sector reduced toxic chemical substance emissions mainly via end-of-pipe treatment. In the meantime, transfer for further management contributed to the reduction of toxic chemical substance emissions in the metal fabrication industry. This occurred because the environmental business market expanded in the 1990s, and the infrastructure for the recycling of metal and other wastes became more efficient. Cleaner production is the main contributor to toxic chemical reduction in the electrical product industry. This implies that the electrical product industry is successful in developing a more environmentally friendly product design and production process.

Insight into the thermal decomposition of kaolinite intercalated with potassium acetate : an evolved gas analysis

The thermal decomposition process of kaolinite–potassium acetate intercalation complex has been studied using simultaneous thermogravimetry coupled with Fourier-transform infrared spectroscopy and mass spectrometry (TG-FTIR-MS). The results showed that the thermal decomposition of the complex took place in four temperature ranges, namely 50–100, 260–320, 320–550, and 650–780 °C. The maximal mass losses rate for the thermal decomposition of the kaolinite–potassium acetate intercalation complex was observed at 81, 296, 378, 411, 486, and 733 °C, which was attributed to (a) loss of the adsorbed water, (b) thermal decomposition of surface-adsorbed potassium acetate (KAc), (c) the loss of the water coordinated to potassium acetate in the intercalated kaolinite, (d) the thermal decomposition of intercalated KAc in the interlayer of kaolinite and the removal of inner surface hydroxyls, (e) the loss of the inner hydroxyls, and (f) the thermal decomposition of carbonate derived from the decomposition of KAc. The thermal decomposition of intercalated potassium acetate started in the range 320–550 °C accompanied by the release of water, acetone, carbon dioxide, and acetic acid. The identification of pyrolysis fragment ions provided insight into the thermal decomposition mechanism. The results showed that the main decomposition fragment ions of the kaolinite–KAc intercalation complex were water, acetone, carbon dioxide, and acetic acid. TG-FTIR-MS was demonstrated to be a powerful tool for the investigation of kaolinite intercalation complexes. It delivers a detailed insight into the thermal decomposition processes of the kaolinite intercalation complexes characterized by mass loss and the evolved gases.

Experimental and numerical study of polymeric foam efficacy in portable water filled barriers

Portable, water filled road safety barriers are used to provide protection and reduce the potential hazard due to errant vehicles in areas where the road conditions change frequently (e.g. near road work sites). As part of an effort to reduce excessive working widths typical of these systems, a study was conducted to assess the effectiveness of introducing polymeric foam filled panels into the design. Surrogate impact tests of a design typical of such as barrier system were conducted utilising a pneumatically powered horizontal impact testing machine up to impact energies of 7.40 kJ. Results of these tests are utilised to examine the barrier behaviour, in addition to being used to validate a couple FE/SPH model of the barrier system. Once validated, the FE/SPH model it utilised as the basis for a parametric study into the efficacy and effects of the inclusion of polymeric foam filled panels on the performance of portable water filled road safety barriers. It was found that extruded polystyrene foam functioned well, with a greater thickness of the foam panel significantly reducing the impacting body velocity as the barrier began to translate.

Marx as a Critical Discourse Analyst : The Genesis of a Critical Method and its Relevance to the Critique of Global Capital (with Phil Graham)

In this paper we identify elements in Marx’s economic and political writings that are relevant to contemporary critical discourse analysis (CDA). We argue that Marx can be seen to be engaging in a form of discourse analysis. We identify the elements in Marx’s historical materialist method that support such a perspective, and exemplify these in longitudinal comparison of Marx’s texts.

An examination of isotherm generation : impact of bottle-point method upon potassium ion exchange with strong acid cation resin

This paper relates to the importance of impact of the chosen bottle-point method when conducting ion exchange equilibria experiments. As an illustration, potassium ion exchange with strong acid cation resin was investigated due to its relevance to the treatment of various industrial effluents and groundwater. The “constant mass” bottle-point method was shown to be problematic in that depending upon the resin mass used the equilibrium isotherm profiles were different. Indeed, application of common equilibrium isotherm models revealed that the optimal fit could be with either the Freundlich or Temkin equations, depending upon the conditions employed. It could be inferred that the resin surface was heterogeneous in character, but precise conclusions regarding the variation in the heat of sorption were not possible. Estimation of the maximum potassium loading was also inconsistent when employing the “constant mass” method. The “constant concentration” bottle-point method illustrated that the Freundlich model was a good representation of the exchange process. The isotherms recorded were relatively consistent when compared to the “constant mass” approach. Unification of all the equilibrium isotherm data acquired was achieved by use of the Langmuir Vageler expression. The maximum loading of potassium ions was predicted to be at least 116.5 g/kg resin.

Use of modal flexibility method to detect damage in suspended cables and the effects of cable parameters

Modal flexibility is a widely accepted technique to detect structural damage using vibration characteristics. Its application to detect damage in long span large diameter cables such as those used in suspension bridge main cables has not received much attention. This paper uses the modal flexibility method incorporating two damage indices (DIs) based on lateral and vertical modes to localize damage in such cables. The competency of those DIs in damage detection is tested by the numerically obtained vibration characteristics of a suspended cable in both intact and damaged states. Three single damage cases and one multiple damage case are considered. The impact of random measurement noise in the modal data on the damage localization capability of these two DIs is next examined. Long span large diameter cables are characterized by the two critical cable parameters named bending stiffness and sag-extensibility. The influence of these parameters in the damage localization capability of the two DIs is evaluated by a parametric study with two single damage cases. Results confirm that the damage index based on lateral vibration modes has the ability to successfully detect and locate damage in suspended cables with 5% noise in modal data for a range of cable parameters. This simple approach therefore can be extended for timely damage detection in cables of suspension bridges and thereby enhance their service during their life spans.

Comparison of active-set method deconvolution and matched-filtering for derivation of an ultrasound transit time spectrum

The quality of ultrasound computed tomography imaging is primarily determined by the accuracy of ultrasound transit time measurement. A major problem in analysis is the overlap of signals making it difficult to detect the correct transit time. The current standard is to apply a matched-filtering approach to the input and output signals. This study compares the matched-filtering technique with active set deconvolution to derive a transit time spectrum from a coded excitation chirp signal and the measured output signal. The ultrasound wave travels in a direct and a reflected path to the receiver, resulting in an overlap in the recorded output signal. The matched-filtering and deconvolution techniques were applied to determine the transit times associated with the two signal paths. Both techniques were able to detect the two different transit times; while matched-filtering has a better accuracy (0.13 μs vs. 0.18 μs standard deviation), deconvolution has a 3.5 times improved side-lobe to main-lobe ratio. A higher side-lobe suppression is important to further improve image fidelity. These results suggest that a future combination of both techniques would provide improved signal detection and hence improved image fidelity.

Promoting articulated action from diverse stakeholders in response to public policy scenarios: A case analysis of the use of ‘scenario improvisation’ method

In this paper we present a novel application of scenario methods to engage a diverse constituency of senior stakeholders, with limited time availability, in debate to inform planning and policy development. Our case study project explores post-carbon futures for the Latrobe Valley region of the Australian state of Victoria. Our approach involved initial deductive development of two ‘extreme scenarios’ by a multi-disciplinary research team, based upon an extensive research programme. Over four workshops with the stakeholder constituency, these initial scenarios were discussed, challenged, refined and expanded through an inductive process, whereby participants took ‘ownership’ of a final set of three scenarios. These were both comfortable and challenging to them. The outcomes of this process subsequently informed public policy development for the region. Whilst this process did not follow a single extant structured, multi-stage scenario approach, neither was it devoid of form. Here, we seek to theorise and codify elements of our process – which we term ‘scenario improvisation’ – such that others may adopt it.

Sustainable life cycles of natural-precursor-derived nanocarbons

Sustainable societal and economic development relies on novel nanotechnologies that offer maximum efficiency at minimal environmental cost. Yet, it is very challenging to apply green chemistry approaches across the entire life cycle of nanotech products, from design and nanomaterial synthesis to utilization and disposal. Recently, novel, efficient methods based on nonequilibrium reactive plasma chemistries that minimize the process steps and dramatically reduce the use of expensive and hazardous reagents have been applied to low-cost natural and waste sources to produce value-added nanomaterials with a wide range of applications. This review discusses the distinctive effects of nonequilibrium reactive chemistries and how these effects can aid and advance the integration of sustainable chemistry into each stage of nanotech product life. Examples of the use of enabling plasma-based technologies in sustainable production and degradation of nanotech products are discussed—from selection of precursors derived from natural resources and their conversion into functional building units, to methods for green synthesis of useful naturally degradable carbon-based nanomaterials, to device operation and eventual disintegration into naturally degradable yet potentially reusable byproducts.

Changes in energy efficiency in Australia: A decomposition of aggregate energy intensity using logarithmic mean Divisia approach

This paper provides an empirical estimation of energy efficiency and other proximate factors that explain energy intensity in Australia for the period 1978-2009. The analysis is performed by decomposing the changes in energy intensity by means of energy efficiency, fuel mix and structural changes using sectoral and sub-sectoral levels of data. The results show that the driving forces behind the decrease in energy intensity in Australia are efficiency effect and sectoral composition effect, where the former is found to be more prominent than the latter. Moreover, the favourable impact of the composition effect has slowed consistently in recent years. A perfect positive association characterizes the relationship between energy intensity and carbon intensity in Australia. The decomposition results indicate that Australia needs to improve energy efficiency further to reduce energy intensity and carbon emissions. © 2012 Elsevier Ltd.

Evaluation of polymeric nanomedicines targeted to PSMA: Effect of ligand on targeting efficiency

Targeted nanomedicines offer a strategy for greatly enhancing accumulation of a therapeutic within a specific tissue in animals. In this study, we report on the comparative targeting efficiency toward prostate-specific membrane antigen (PSMA) of a number of different ligands that are covalently attached by the same chemistry to a polymeric nanocarrier. The targeting ligands included a small molecule (glutamate urea), a peptide ligand, and a monoclonal antibody (J591). A hyperbranched polymer (HBP) was utilized as the nanocarrier and contained a fluorophore for tracking/analysis, whereas the pendant functional chain-ends provided a handle for ligand conjugation. Targeting efficiency of each ligand was assessed in vitro using flow cytometry and confocal microscopy to compare degree of binding and internalization of the HBPs by human prostate cancer (PCa) cell lines with different PSMA expression status (PC3-PIP (PSMA+) and PC3-FLU (PSMA−). The peptide ligand was further investigated in vivo, in which BALB/c nude mice bearing subcutaneous PC3-PIP and PC3-FLU PCa tumors were injected intravenously with the HBP-peptide conjugate and assessed by fluorescence imaging. Enhanced accumulation in the tumor tissue of PC3-PIP compared to PC3-FLU highlighted the applicability of this system as a future imaging and therapeutic delivery vehicle.