The kinetics of the gas-phase reactions of selected monoterpenes and cyclo-alkenes with ozone and the NO3 radical

The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.

Magnetic characterization of ferrihydrite nanoparticles synthesized by hydrolysis of Fe metal-organic precursor

We investigate the formation of ferrihydrite nanoparticles (NPs) by hydrolysis of the Fe(III) alkoxide Fe(O(t)Bu)(3). Controlled amounts of water, up to 3.0 vol%, were added to the precursor solution yielding a series of hydrolyzed samples ranging from P0.0 (the unreacted precursor) to P3.0. X-ray diffraction (XRD) analysis evidenced the formation of high-crystalline ferrihydrite NP in sample P3.0, with grain size estimate of about 3.2 nm. The transition from the molecular precursor to the formation of crystalline magnetic NPs was followed through magnetization measurements M(T) and M(H), as well as Mossbauer spectroscopy (MS). M(T) measurements indicate a paramagnetic (PM) behavior for sample P0.0, characteristic of binuclear Fe-O-Fe units, which evolves to a superparamagnetic (SPM) behavior, with an energy barrier for the blocking process estimated for sample P3.0 as E(a) = 4.9 x 10(-21) J (E(a)/k(B) = 355 K), resulting in a high effective anisotropy constant K(eff) = 290 kJ/m(3). Magnetization loops at 5 K progressively change from PM-like to ferromagnetic-like shape upon increasing the hydrolysis process, although hysteresis (H(c) approximate to 500 Oe) only is apparent for P2.0 and higher. MS spectra at room temperature are PM/SPM doublets for all samples, while the MS spectra at T = 4.2 K reveal increasingly well-defined magnetic ordering as hydrolysis of the precursor stepwise progresses until well-crystallized ferrihydrite particles are formed. (C) 2008 Elsevier B.V. All rights reserved.

Two-photon absorption spectrum of the photoinitiator Lucirin TPO-L

Two-photon absorption induced polymerization provides a powerful method for the fabrication of intricate three-dimensional microstructures. Recently, Lucirin TPO-L was shown to be a photoinitiator with several advantageous properties for two-photon induced polymerization. Here we measure the two-photon absorption cross-section spectrum of Lucirin TPO-L, which presents a maximum of 1.2 GM at 610 nm. Despite its small two-photon absorption cross-section, it is possible to fabricate excellent microstructures by two-photon polymerization due to the high polymerization quantum yield of Lucirin TPO-L. These results indicate that optimization of the two-photon absorption cross-section is not the only material parameter to be considered when searching for new photoinitiators for microfabrication via two-photon absorption.

Ability of Ru complexes for ROMP tuned through a combination of phosphines and amines

Polynorbonerne with high molecular weight was obtained via ring opening metathesis polymerization using catalysts derived from [RuCl(2)(PPh(2)Bz)(2) L] (1 for L = PPh(2) Bz; 2 for L = piperidine) type of complexes when in the presence of ethyl diazoacetate in CHCl(3). The polymer precipitated within a few minutes at 50 degrees C when using 1 with ca. 50% yield ([NBE]/[Ru] = 5000). Regarding 2, for either 30 min at 25 C or 5 min at 50 degrees C, more than 90% of yields are obtained; and at 50 C for 30 min a quantitative yield is obtained. The yield and PDI values are sensitive to the [NBE]/[Ru] ratio. The reaction of 1 with either isonicotinamide or nicotinamide produces six-coordinated complexes of [RuCl(2)(PPh(2)Bz)(2)(L)(2)] type, which are almost inactive and produce only small amounts of polymers at 50 C for 30 min. Thus, we Concluded that the novel complexes show very distinct reactivities for ROMP of NBE. This has been rationalized on account of a combination of synergistic effects of the phosphine-amine ancillary ligands. (C) 2009 Elsevier B.V. All rights reserved.

Analysis of cultural conflict in the development of web-enabled information systems

The advent of the World Wide Web (WWW) and the emergence of Internet commerce have given rise to the web as a medium of information exchange. In recent years, the phenomenon has affected the realm of transaction processing systems, as organizations are moving from designing web pages for marketing purposes, to web-based applications that support business-to-business (WEB) and business-to-consumer (B2C) interactions, integrated with databases and other back-end systems (Isakowitz, Bieber et al., 1998). Furthermore, web-enabled applications are increasingly being used to facilitate transactions even between various business units within a single enterprise. Examples of some of the more popular web-enabled applications in use today include airline reservation systems, internet banking, student enrollment systems in universities, and Human Resource (HR) and payroll systems. The prime motive behind the adoption of web-enabled applications are productivity gains due to reduced processing time, decrease in the usage of paper-based documentation and conventional modes of communication (such as letters, fax, or telephone), and improved quality of services to clients. Indeed, web-based solutions are commonly referred to as customer-centric (Li, 2000), which means that they provide user interfaces that do not necessitate high level of computer proficiency. Thus, organizations implement such systems to streamline routine transactions and gain strategic benefits in the process (Nambisan & Wang, 1999), though the latter are to be expected in the long-term. Notwithstanding the benefits of web technology adoption, the web has ample share of challenges for initiators and developers. Many of these challenges are associated with the unique nature of web-enabled applications. Research in the area of web-enabled information systems has revealed several differences with traditional applications. These differences exist with regards to system development methodology, stakeholder involvement, tasks, and technology (Nazareth, 1998). According to Fraternali (1999), web applications are commonly developed using an evolutionary prototyping approach, whereby the simplified version of the application is deployed as a pilot first, in order to gather user feedback. Thus, web-enabled applications typically undergo continuous refinement and evolution (Ginige, 1998; Nazareth, 1998; Siau, 1998; Standing, 2001). Prototype-based development also leads web-enabled information systems to have much shorter development life cycles, but which, unlike traditional applications, are regrettably developed in a rather adhoc fashion (Carstensen & Vogelsang, 2001). However, the principal difference between the two kinds of applications lies in the broad and diverse group of stakeholders associated with web-based information systems (Gordijn, Akkermans, et al., 2000; Russo, 2000; Earl & Khan, 2001; Carter, 2002; Hasselbring, 2002; Standing, 2002; Stevens & Timbrell, 2002). Stakeholders, or organizational members participating in a common business process (Freeman, 1984), vary in their computer competency, business knowledge, language and culture. This diversity is capable of causing conflict between different stakeholder groups with regards to the establishment of system requirements (Pouloudi & Whitley, 1997; Stevens & Timbrell, 2002). Since, web-based systems transcend organizational, departmental, and even national boundaries, the issue of culture poses a significant challenge to the web systems’ initiators and developers (Miles & Snow, 1992; Kumar & van Dissel, 1996; Pouloudi & Whitley, 1996; Li & Williams, 1999).

Management and business issues for B2B eCommerce implementation

Until recently little research had been undertaken into the process of eCommerce implementation, especially in relation to the implementation of business-to-business (B2B) relationships. Given the complexity of this process we have, in this paper, endeavoured to contribute to what we perceive as a gap in the body of theory surrounding the implementation process in the extant business-to-business literature. We describe the findings of a series of multiple case studies comprising ten major Australian eCommerce initiators. In addition to confirming our earlier finding of the importance of nontechnical factors for the success of the implementation process we also present, through our case studies, the various management and business issues associated with the success or otherwise of B2B eCommerce implementation.

International examples of large-scale systems-theory and practice IV: B2B e-commerce implementation in the Australian context

Two of the most commonly used classifications in IS research are the factor approach and the process approach. While many studies of IS implementation are undertaken using a factor approach, little research so far examines the process of e-commerce implementation, especially in relation to the implementation of e-commerce in business-to-business (B2B) relationships. A holistic understanding of implementation which combines both the factor and process approaches using a case study method, is suggested as particularly suitable because of its ability to capture the reality of e-commerce implementation in an organisation's natural environment and in much greater detail than is possible using one of these approaches alone. In this paper, therefore, we endeavour to contribute to what we perceive as a gap in the body of theory surrounding the implementation process in the business-to-business e-commerce literature. We describe the findings of multiple case studies involving ten major Australian e-commerce initiators. In addition to confirming our earlier finding of the importance of non-technical factors for the success of the implementation process we also present, through our case studies, the various management and business issues associated with the success or failure of B2B e-commerce implementation.

Effect of cell characteristics on the compressive deformation behavior of a closed-cell aluminium

In this study, the mechanical properties of a closed-cell aluminium foam have been investigated by compressive tests. The deformation behaviors of the aluminium foams were studied using X-ray microtomography (XMT). Aluminium foam samples with various cell size distributions and cell
morphologies were intentionally selected to investigate the effect of the cell characteristics on the deformation behaviors. Results indicated that the deformation of the aluminium foams under compressive loading was localized in narrow continuous deformation bands having widths of order of a cell diameter. The cells in the deformation bands collapsed by a mixed deformation mechanism, which includes mainly bending, and also minor buckling and yielding as well. Different fractions of the three deformation modes led to variations in the peak stress and energy absorption for different foam samples with the same density. It was also found that the cell morphology affected the deformation mechanism significantly, whilst the cell size showed little influence. Those cells with defects such as corrugations, curvatures and non-uniformities in the wall thickness were the initiators of the deformation bands of the aluminium foam.

Phenomenological inquiry into the experience of web project managers

The advent of the Internet and the World Wide Web has been instrumental in bringing about the growth in the implementation of web-based information systems (WBIS). Such systems are designed with the aim of improving productivity, data accuracy, and the reduction of paperwork and administrative overheads. Moreover, unlike their conventional non-web-based predecessors, the WBIS are commonly aimed at users who are casual and untrained, geographically distributed and non-homogenous. The dissemination of WBIS necessitates additional infrastructure support in the form of a security system, workflow and transaction management, and web administration. WBIS are commonly developed using an evolutionary approach, whereby the version of the application, acquired from the vendor, is first deployed as a pilot, in order to gather feedback from the target users before the evolutionary cycles commence. While a number of web development methodologies have been proposed by existing research, there is a dearth of empirical evidence that elucidates the experiences of project initiators in pursuing the evolution of web services, a process that undoubtedly involves dealing with stakeholder issues. This research project presents a phenomenological investigation of the experiences of project managers with the implementation of web-based employee service systems (ESS), a domain that has witnessed a sharp growth in Australia in recent times. However, the project managers’ rich, multidimensional account of their experiences with the implementation of ESS revealed the social obstacles and fragility of intra-organizational relationships that demanded a cautious and tactful approach. Thus, the study provides a socio-organizational perspective to web projects in contrast to the functionalist paradigm of current web development methodologies. The research also confirms that consideration of the concerns of stakeholders by project managers is crucial to the successive cycles of ESS evolution. Project managers address stakeholder concerns by pursuing actions that are aimed at encouraging ESS usage, but at the same time, such actions can have consequences necessitating subsequent iterations of system enhancement and improvement. Finally, the research also discovered that despite the different socio-political climate prevalent in various organizations, in which ESS are being implemented, the experiences of project managers in dealing with stakeholder concerns can be captured and independently confirmed in terms of their perceived relevance and usefulness in problem-solving within the application domain.

Strain rate effects on the energy absorption of rapidly manufactured composite tubes

Quasi-static and intermediate rate axial crush tests were conducted on tubular specimens of Carbon/Epoxy (Toray T700/G83C) and Glass/Polypropylene (Twintex). The quasi-static tests were conducted at 10 mm/min (1.67 x 10¯⁴ m/s); five different crush initiators were used. Tests at intermediate rates were performed at speeds of 0.25, 0.5, 0.75, 1, 2, and 4m/s. Modes of failure and specific energy absorption (SEA) values were studied. The highest SEA measured was 86 kJ/kg. This value was observed using Carbon/Epoxy samples at quasi static rates with a 45° chamfer initiator. The highest energy absorption for Twintex tubes was observed to be 57.56 kJ/kg during 45° chamfer initiated tests at 0.25 m/s. Compared with steel and aluminium, SEA values of 15 and 30 kJ/kg, respectively, the benefits of using composite materials in crash structures become apparent.

Ionic liquid electrolyte for lithium metal batteries : physical, electrochemical, and interfacial studies of N-Methyl-N-butylmorpholinium Bis(fluorosulfonyl)imide

The ionic liquid (IL) N-methyl-N-butylmorpholinium bis(fluorosulfonyl)imide (C₄mmor FSI) is examined from physical and electrochemical perspectives. Pulsed field gradient NMR spectroscopy shows that ion diffusivities are low compared with similar, non-ethereal ILs. Ionicity values indicate that above room temperature, less than 50% of ions contribute to conductivity.

Lithium cycling in symmetrical cells using a C₄mmor FSI-based electrolyte is best demonstrated at elevated temperatures. Specific capacities of 130 mAh g⁻¹ are achieved in a Li−LiFePO₄ battery at 85 °C. FT-IR spectroscopic investigations of lithium electrodes suggest the presence of alkoxide species in the solid electrolyte interphase (SEI), implying a ring-opening reaction of C₄mmor with lithium metal. In contrast, the SEI derived from N-methyl-N-propylpiperidinium FSI lacks the alkoxide signature but shows signs of alkyl unsaturation, and the activation energy for Li+ transport through this SEI is slightly lower than that for the C₄mmor-derived SEI. Our detailed findings give insight into the capabilities and limitations of rechargeable lithium metal batteries utilizing a C₄mmor FSI electrolyte.

Crosslinking neat ultrathin films and nanofibres of pH-responsive poly(acrylic acid) by UV radiation

Electrospun polyelectrolyte hydrogel nanofibres are being developed for many applications including artificial muscles, scaffolds for tissue engineering, wound dressings and controlled drug release. For electrospun polyelectrolytes, a post-spinning crosslinking process is necessary for producing a hydrogel. Typically, radiation or thermal crosslinking routines are employed that require multifunctional crosslinking molecules and crosslink reaction initiators (free radical producers). Here, ultraviolet subtype-C (UVC) radiation was employed to crosslink neat poly(acrylic acid) (PAA) nanofibres and films to different crosslink densities. Specific crosslink initiators or crosslinking molecules are not necessary in this fast and simple process providing an advantage for biological applications. Scanning probe microscopy was used for the first time to measure the dry and wet dimensions of hydrogel nanofibres. The diameters of the swollen fibres decrease monotonically with increasing UVC radiation time. The fibres could be reversibly swollen/contracted by treatment with solutions of varying pH, demonstrating their potential as artificial muscles. The surprising success of UVC radiation exposure to achieve chemical crosslinks without a specific initiator molecule exploits the ultrathin dimensions of the PAA samples and will not work with relatively thick samples.

RNAi mediated Tiam1 gene knockdown inhibits invasion of retinoblastoma

T lymphoma invasion and metastasis protein (Tiam1) is up-regulated in variety of cancers and its expression level is related to metastatic potential of the type of cancer. Earlier, Tiam1 was shown to be overexpressed in retinoblastoma (RB) and we hypothesized that it was involved in invasiveness of RB. This was tested by silencing Tiam1 in RB cell lines (Y79 and Weri-Rb1) using siRNA pool, targeting different regions of Tiam1 mRNA. The cDNA microarray of Tiam1 silenced cells showed gene regulations altered by Tiam1 were predominantly on the actin cytoskeleton interacting proteins, apoptotic initiators and tumorogenic potential targets. The silenced phenotype resulted in decreased growth and increased apoptosis with non-invasive characteristics. Transfection of full length and N-terminal truncated construct (C1199) clearly revealed membrane localization of Tiam1 and not in the case of C580 construct. F-actin staining showed the interaction of Tiam1 with actin in the membrane edges that leads to ruffling, and also imparts varying invasive potential to the cell. The results obtained from our study show for the first time that Tiam1 modulates the cell invasion, mediated by actin cytoskeleton remodeling in RB.

Book review : Citizen voices: performing public participation in science and environment communication

In Citizen Voices Phillips, Carvalho and Doyle present a collection of articles exploring the meaning of “citizens” and their role as initiators of communication on science and as actors in formal public engagement exercises involved in science governance. Focusing on the dialogic process, the articles provide empirical insight into the effect of citizen voices on participatory decision-making and a range of related theories and methodologies.

Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products