On the importance of an acid additive in the synthesis of pyrido[1,2-a]benzimidazoles by direct copper-catalyzed amination

Pyrido[1,2-a]benzimidazoles1, 2a are interesting compounds both from the viewpoint of medicinal chemistry2–7 (solubility,7 DNA intercalation3) and materials chemistry8 (fluorescence). Of note among the former is the antibiotic drug Rifaximin,5 which contains this heteroaromatic core. The classical synthetic approach for the assembly of pyrido[1,2-a]benzimidazoles is by [3+3] cyclocondensation of benzimidazoles containing a methylene group at C2 with appropriate bielectrophiles.2a However, these procedures are often low-yielding, involve indirect/lengthy sequences, and/or provide access to a limited range of products, primarily providing derivatives with substituents located on the pyridine ring (A ring, Scheme 1).2–4 Theoretically, a good alternative synthetic method for the synthesis of pyrido[1,2-a]benzimidazoles with substituents in the benzene ring (C ring) should be accessible by intramolecular transition-metal-catalyzed CN bond formation in N-(2-chloroaryl)pyridin-2-amines, based on chemistry recently developed in our research group.9 These substrates themselves are easily available through SNAr or selective Pd-catalyzed amination10 of 2-chloropyridine with 2-chloroanilines.11 If a synthetic procedure that eliminated the need for preactivation of the 2-position of the 2-chloroarylamino entity could be developed, this would be even more powerful, as anilines are more readily commercially available than 2-chloroanilines. Therefore the synthesis of pyrido[1,2-a]benzimidazoles (4) by a transition-metal-catalyzed intramolecular CH amination approach from N-arylpyridin-2-amines (3) was explored (Scheme 1).

Critical reflections on the use of participatory methodologies to build evaluation capacities in international development organisations

There has been a greater focus on strengthening evaluation capacity building (ECB) within development organisations in recent years. This can be attributed in part to the growing appreciation of the value of participatory and collaborative forms of evaluation. Evaluation is increasingly seen as an ongoing learning process and an important means of strengthening capacity and improving organisational performance (Horton et al., 2003:7). While there are many benefits of using participatory methodologies in ECB projects, our experiences and a review of the literature in this area highlight the many challenges, issues and contradictions that can affect the success of such ECB efforts. We discuss these issues, drawing on our learnings from the ongoing participatory action research (PAR) project 'Assessing Communication for Social Change’ (AC4SC). This four year project, which began in 2007, is a collaboration between communication and development academics and evaluation specialists from two Australian universities and communication for development practitioners and monitoring and evaluation (M&E) staff in the NGO Equal Access Nepal (EAN). The aim is to develop, implement, and evaluate a participatory methodology for assessing the social change impacts of community radio programs produced by EAN. It builds on previous projects that used ethnographic action research (EAR) methodology (Tacchi et al., 2007).

Critical reflections on the use of participatory methodologies to build evaluation capacities in international development organisations

"In this chapter the authors present a critique of Participatory Evaluation as worked in development projects, in this case, in Nepal. The article works between established claims that Participatory Evaluation builds capacity at programmatic and organisational levels, and the specific experiences of these claims in the authors’ current work. They highlight the need to address key difficulties such as high turn-over of staff and resulting loss of capacity to engage in Participatory Evaluation, and the difficulty of communication between academic as compared with local practical wisdoms. A key issue is the challenge of addressing the inevitable issues of power inequities that such approaches encounter. While Participatory Evaluation has been around for some time, it has only enjoyed more widespread recognition of its value in comparatively recent times, with its uptake in international development environments. To this extent, the practice is still in its early stages of development, and Jo, June and Michael’s work contributes to strengthening and more comprehensively understanding it. With regard to the meta-theme of this publication, this chapter is an example of how context not only influences the methodology to be used and the praxis of how it is to be used, but contributes to early explication of the core nature of an emerging methodology."

Effect of Al content on the structure of Al-substituted goethite : a micro-Raman spectroscopic study

The characterization of X-ray diffraction, X-ray fluorescence, and field emission scanning electron microscope were used to confirm the successful preparation of Al-substituted goethite with different Al content. The micro-Raman spectroscopy was utilized to investigate the effect of Al content on the goethite lattice. The results show that all the feature bands of goethite shifted to high wavenumbers after the occurrence of Al substitution for Fe in the structure of goethite. The shift of wavenumber shows a good linear relationship as a function of increasing Al content especially for the band at 299 cm−1 (R2 = 0.9992). The in situ Raman spectroscopy of thermally treated goethite indicated that the Al substitution not only hinders the transformation of goethite, but also retarded the crystallization of thermally formed hematite. All the results indicated that Raman spectrum displayed an excellent performance in characterizing Al-substituted goethite, which implied the promising application in other substituted metal oxides or hydroxides.

On the (in)security of IDEA in various hashing modes

In this article, we study the security of the IDEA block cipher when it is used in various simple-length or double-length hashing modes. Even though this cipher is still considered as secure, we show that one should avoid its use as internal primitive for block cipher based hashing. In particular, we are able to generate instantaneously free-start collisions for most modes, and even semi-free-start collisions, pseudo-preimages or hash collisions in practical complexity. This work shows a practical example of the gap that exists between secret-key and known or chosen-key security for block ciphers. Moreover, we also settle the 20-year-old standing open question concerning the security of the Abreast-DM and Tandem-DM double-length compression functions, originally invented to be instantiated with IDEA. Our attacks have been verified experimentally and work even for strengthened versions of IDEA with any number of rounds.

Laboratory study on the performance of recycled concrete aggregates blended with reclaimed asphalt pavement as pavement granular material

Production of recycled concrete aggregates (RCA) from construction and demolition (C&D) waste has become popular all over the world since the availability of land spaces are limited to dispose. Therefore it is important to seek alternative applications for RCA. The use of RCA in base and sub-base layers in granular pavement is a viable solution. In mechanistic pavement design, rutting (permanent deformation) is considered as the major failure mechanisms of the pavement. The rutting is the accumulation of permanent deformation of pavement layers caused by the repetitive vehicle load. In Queensland, Australia, it is accepted to have the maximum of 20% of reclaimed asphalt pavement (RAP) in RCA and therefore, it is important to investigate the effect of RAP on the permanent deformation properties of RCA. In this study, a series of repeated load triaxial (RLT) tests were conducted on RCA blended with different percentage of RAP to investigate the permanent deformation and resilient modulus properties of RCA. The vertical deformation and resilient modulus values were used to determine the response of RCA for the cyclic loading under standard pressure and loading conditions.

On the security of PAS (predicate-based authentication service)

Recently a new human authentication scheme called PAS (predicate-based authentication service) was proposed, which does not require the assistance of any supplementary device. The main security claim of PAS is to resist passive adversaries who can observe the whole authentication session between the human user and the remote server. In this paper we show that PAS is insecure against both brute force attack and a probabilistic attack. In particular, we show that its security against brute force attack was strongly overestimated. Furthermore, we introduce a probabilistic attack, which can break part of the password even with a very small number of observed authentication sessions. Although the proposed attack cannot completely break the password, it can downgrade the PAS system to a much weaker system similar to common OTP (one-time password) systems.

Age and curing effect on the bond strength of thin bed concrete masonry with polymer cement mortar

Bond characteristics of masonry are partly affected by the type of mortar used, the techniques of dispersion of mortar and the surface texture of the concrete blocks. Additionally it is understood from the studies on conventional masonry, the bond characteristics are influenced by masonry age and curing methods as well as dryness/dampness at the time of testing. However, all these effects on bond for thin bed masonry containing polymer cement mortar are not well researched. Therefore, the effect of ageing and curing method on bond strength of masonry made with polymer cement mortar was experimentally investigated as part of an ongoing bond strength research program on thin bed concrete masonry at Queensland University of technology. This paper presents the experimental investigation of the flexural and shears bond characteristics of thin bed concrete masonry of varying age/ curing methods. Since, the polymer cement mortar is commonly used in thin bed masonry; bond development through two different curing conditions (dry/wet) was investigated in this research work. The results exhibit that the bond strength increases with the age under the wet and dry curing conditions; dry curing produce stronger bond and is considered as an advantage towards making this form of thin bed masonry better sustainable.

Heat transfer measurements on the first experimental layer of the FIRE II reentry vehicle in expansion tubes

The present study focused on simulating a trajectory point towards the end of the first experimental heatshield of the FIRE II vehicle, at a total flight time of 1639.53s. Scale replicas were sized according to binary scaling and instrumented with thermocouples for testing in the X1 expansion tube, located at The University of Queensland. Correlation of flight to experimental data was achieved through the separation, and independent treatment of the heat modes. Preliminary investigation indicates that the absolute value of radiant surface flux is conserved between two binary scaled models, whereas convective heat transfer increases with the length scale. This difference in the scaling techniques result in the overall contribution of radiative heat transfer diminishing to less than 1% in expansion tubes from a flight value of approximately 9-17%. From empirical correlation's it has been shown that the St √Re number decreases, under special circumstances, in expansion tubes by the percentage radiation present on the flight vehicle. Results obtained in this study give a strong indication that the relative radiative heat transfer contribution in the expansion tube tests is less than that in flight, supporting the analysis that the absolute value remains constant with binary scaling.

An algebraic analysis of trivium ciphers based on the boolean satisfiability problem

Trivium is a stream cipher candidate of the eStream project. It has successfully moved into phase three of the selection process under the hardware category. No attacks faster than the exhaustive search have so far been reported on Trivium. Bivium-A and Bivium-B are simplified versions of Trivium that are built on the same design principles but with two registers. The simplified design is useful in investigating Trivium type ciphers with a reduced complexity and provides insight into effective attacks which could be extended to Trivium. This paper focuses on an algebraic analysis which uses the boolean satisfiability problem in propositional logic. For reduced variants of the cipher, this analysis recovers the internal state with a minimal amount of keystream observations.

Influence of tilt and surface roughness on the outflow wind field of an impinging jet

A physical and numerical steady flow impinging jet has been used to simulate the bulk characteristics of a downburst-like wind field. The influence of downdraft tilt and surface roughness on the ensuing wall jet flow has been investigated. It was found that a simulated downdraft impinging the surface at a non-normal angle has the potential for causing larger structural loads than the normal impingement case. It was also found that for the current impinging jet simulations, surface roughness played a minor role in determining the storm maximum wind structure, but this influence increased as the wall jet diverged. However, through comparison with previous research it was found that the influence of surface roughness is Reynolds number dependent and therefore may differ from that reported herein for full-scale downburst cases. Using the current experimental results an empirical model has been developed for laboratory-scale impinging jet velocity structure that includes the influence of both jet tilt and surface roughness.

Managing creativity on the margins : a comparative study of Beijing’s Songzhuang Art District and Hangzhou’s White Horse Lake Creative Eco-City

In the past decade the ‘creative cluster’ has become a driver of urban renewal in China. Many cluster developments attract human capital and investment to post-industrial spaces. This paper looks at two developments which are more post-agricultural than post-industrial: the first is Songzhuang, a large scale contemporary art community situated on the eastern fringe of Beijing, the second is Hangzhou’s White Horse Lake Creative Eco-City, a ‘mixed variety’ cluster model which integrates elements of art, fashion, design and animation. The common factor in both cases is how they came into existence. In both districts urban creative workers moved into a rural environment. Drawing on interviews with planners, officials, and residents we investigate the challenges of sustaining such fringe clusters.

Effect of real support conditions on the shear strength of hollow flange channel beams

This paper presents the details of experimental studies on the effect of real support conditions on the shear strength of LiteSteel beams (LSB). The LSB has a unique shape of a channel beam with two rectangular hollow flanges, made using a unique manufacturing process. In some applications in the building industry LSBs are used with only one web side plate (WSP) at their supports and are not used with full height web side plates (WSP) at their supports. Past research studies showed that theses real support connections did not provide simply supported conditions. Many studies have been carried out to evaluate the behaviour and design of LSBs with simply supported conditions subject to pure bending and predominant shear actions. To date, however, no investigation has been conducted into the effect of real support conditions on the shear strength of LSBs. Hence detailed experimental studies were undertaken to investigate the shear behaviour and strength of LSBs with real support conditions. A total of 28 experimental tests were conducted as part of the studies. Simply supported test specimens of LSBs with aspect ratios of 1.0 and 1.5 were loaded at mid-span until failure. It was found that the effect of using one WSP on the shear behaviour of LSB is significant and there is about 25% shear capacity reduction due to the lateral movement of the bottom flange at the supports. Shear capacity of LSB was also found to decrease when full height WSPs were not used. Suitable support connections were developed to improve the shear capacity of LSBs based on test results.

On the maturity of open source BPM systems

In this Article, Petia Wohed, Arthur H. M. ter Hofstede, Nick Russell, Birger Andersson, and Wil M. P. van der Aalst present the results of their examination of existing open source BPM systems. Their conclusions are illuminating for both Open Source developers as well as the user community. Read their Article for the details of their study.