Three-dimensional hydrogen-bonded structures in the 1:1 proton-transfer compounds of L-tartaric acid with the associative-group monosubstituted pyridines 3-minopyridine, 3-carboxypyridine (nicotinic acid) and 2-carboxypyridine (picolinic acid).

The 1:1 proton-transfer compounds of L-tartaric acid with 3-aminopyridine [3-aminopyridinium hydrogen (2R,3R)-tartrate dihydrate, C5H7N2+·C4H5O6-·2H2O, (I)], pyridine-3-carboxylic acid (nicotinic acid) [anhydrous 3-carboxypyridinium hydrogen (2R,3R)-tartrate, C6H6NO2+·C4H5O6-, (II)] and pyridine-2-carboxylic acid [2-carboxypyridinium hydrogen (2R,3R)-tartrate monohydrate, C6H6NO2+·C4H5O6-·H2O, (III)] have been determined. In (I) and (II), there is a direct pyridinium-carboxyl N+-HO hydrogen-bonding interaction, four-centred in (II), giving conjoint cyclic R12(5) associations. In contrast, the N-HO association in (III) is with a water O-atom acceptor, which provides links to separate tartrate anions through Ohydroxy acceptors. All three compounds have the head-to-tail C(7) hydrogen-bonded chain substructures commonly associated with 1:1 proton-transfer hydrogen tartrate salts. These chains are extended into two-dimensional sheets which, in hydrates (I) and (III) additionally involve the solvent water molecules. Three-dimensional hydrogen-bonded structures are generated via crosslinking through the associative functional groups of the substituted pyridinium cations. In the sheet struture of (I), both water molecules act as donors and acceptors in interactions with separate carboxyl and hydroxy O-atom acceptors of the primary tartrate chains, closing conjoint cyclic R44(8), R34(11) and R33(12) associations. Also, in (II) and (III) there are strong cation carboxyl-carboxyl O-HO hydrogen bonds [OO = 2.5387 (17) Å in (II) and 2.441 (3) Å in (III)], which in (II) form part of a cyclic R22(6) inter-sheet association. This series of heteroaromatic Lewis base-hydrogen L-tartrate salts provides further examples of molecular assembly facilitated by the presence of the classical two-dimensional hydrogen-bonded hydrogen tartrate or hydrogen tartrate-water sheet substructures which are expanded into three-dimensional frameworks via peripheral cation bifunctional substituent-group crosslinking interactions.

On the affinity of Chuaria–Tawuia complex : a multidisciplinary study

In this study, biometric and structural engineering tool have been used to examine a possible relationship within Chuaria–Tawuia complex and micro-FTIR (Fourier Transform Infrared Spectroscopy) analyses to understand the biological affinity of Chuaria circularis Walcott, collected from the Mesoproterozoic Suket Shales of the Vindhyan Supergroup and the Neoproterozoic Halkal Shales of the Bhima Group of peninsular India. Biometric analyses of well preserved carbonized specimens show wide variation in morphology and uni-modal distribution. We believe and demonstrate to a reasonable extent that C. circularis most likely was a part of Tawuia-like cylindrical body of algal origin. Specimens with notch/cleft and overlapping preservation, mostly recorded in the size range of 3–5 mm, are of special interest. Five different models proposed earlier on the life cycle of C. circularis are discussed. A new model, termed as ‘Hybrid model’ based on present multidisciplinary study assessing cylindrical and spherical shapes suggesting variable cell wall strength and algal affinity is proposed. This model discusses and demonstrates varied geometrical morphologies assumed by Chuaria and Tawuia, and also shows the inter-relationship of Chuaria–Tawuia complex. Structural engineering tool (thin walled pressure vessel theory) was applied to investigate the implications of possible geometrical shapes (sphere and cylinder), membrane (cell wall) stresses and ambient pressure environment on morphologically similar C. circularis and Tawuia. The results suggest that membrane stresses developed on the structures similar to Chuaria–Tawuia complex were directly proportional to radius and inversely proportional to the thickness in both cases. In case of hollow cylindrical structure, the membrane stresses in circumferential direction (hoop stress) are twice of the longitudinal direction indicating that rupture or fragmentation in the body of Tawuia would have occurred due to hoop stress. It appears that notches and discontinuities seen in some of the specimens of Chuaria may be related to rupture suggesting their possible location in 3D Chuaria. The micro-FTIR spectra of C. circularis are characterized by both aliphatic and aromatic absorption bands. The aliphaticity is indicated by prominent alkyl group bands between 2800–3000 and 1300–1500 cm−1. The prominent absorption signals at 700–900 cm−1 (peaking at 875 and 860 cm−1) are due to aromatic CH out of plane deformation. A narrow, strong band is centred at 1540 cm−1 which could be COOH band. The presence of strong aliphatic bands in FTIR spectra suggests that the biogeopolymer of C. circularis is of aliphatic nature. The wall chemistry indicates the presence of ‘algaenan’—a biopolymer of algae.

The educational affordances of generative media in arts education

Network Jamming systems provide real-time collaborative media performance experiences for novice or inexperienced users. In this paper we will outline the theoretical and developmental drivers for our Network Jamming software, called jam2jam. jam2jam employs generative algorithmic techniques with particular implications for accessibility and learning. We will describe how theories of engagement have directed the design and development of jam2jam and show how iterative testing cycles in numerous international sites have informed the evolution of the system and its educational potential. Generative media systems present an opportunity for users to leverage computational systems to make sense of complex media forms through interactive and collaborative experiences. Generative music and art are a relatively new phenomenon that use procedural invention as a creative technique to produce music and visual media. These kinds of systems present a range of affordances that can facilitate new kinds of relationships with music and media performance and production. Early systems have demonstrated the potential to provide access to collaborative ensemble experiences to users with little formal musical or artistic expertise.This presentation examines the educational affordances of these systems evidenced by field data drawn from the Network Jamming Project. These generative performance systems enable access to a unique kind of music/media’ ensemble performance with very little musical/ media knowledge or skill and they further offer the possibility of unique interactive relationships with artists and creative knowledge through collaborative performance. Through the process of observing, documenting and analysing young people interacting with the generative media software jam2jam a theory of meaningful engagement has emerged from the need to describe and codify how users experience creative engagement with music/media performance and the locations of meaning. In this research we observed that the musical metaphors and practices of ‘ensemble’ or collaborative performance and improvisation as a creative process for experienced musicians can be made available to novice users. The relational meanings of these musical practices afford access to high level personal, social and cultural experiences. Within the creative process of collaborative improvisation lie a series of modes of creative engagement that move from appreciation through exploration, selection, direction toward embodiment. The expressive sounds and visions made in real-time by improvisers collaborating are immediate and compelling. Generative media systems let novices access these experiences with simple interfaces that allow them to make highly professional and expressive sonic and visual content simply by using gestures and being attentive and perceptive to their collaborators. These kinds of experiences present the potential for highly complex expressive interactions with sound and media as a performance. Evidence that has emerged from this research suggest that collaborative performance with generative media is transformative and meaningful. In this presentation we draw out these ideas around an emerging theory of meaningful engagement that has evolved from the development of network jamming software. Primarily we focus on demonstrating how these experiences might lead to understandings that may be of educational and social benefit.

One-dimensional hydrogen-bonded structures in the 1:1 proton-transfer salts of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine

The crystal structures of the 1:1 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases diisopropylamine and hexamethylenetetramine, viz. diisopropylaminium 2-carboxy-4,5-dichlorobenzoate (1) and hexamethylenetetraminium 2-carboxy-4,5-dichlorobenzoate hemihydrate (2), have been determined. Crystals of both 1 and 2 are triclinic, space group P-1, with Z = 2 in cells with a = 7.0299(5), b = 9.4712(7), c = 12.790(1)Å, α = 99.476(6), β = 100.843(6), γ = 97.578(6)o (1) and a = 7.5624(8), b = 9.8918(8), c = 11.5881(16)Å, α = 65.660(6), β = 86.583(4), γ = 86.987(8)o (2). In each, one-dimensional hydrogen-bonded chain structures are found: in 1 formed through aminium N+-H...Ocarboxyl cation-anion interactions. In 2, the chains are formed through anion carboxyl O...H-Obridging water interactions with the cations peripherally bound. In both structures, the hydrogen phthalate anions are essentially planar with short intra-species carboxylic acid O-H...Ocarboxyl hydrogen bonds [O…O, 2.381(3) Å (1) and 2.381(8) Å (2)].

Technical note : modelling a complex micro-multileaf collimator using the standard BEAMnrc distribution

Purpose: The component modules in the standard BEAMnrc distribution may appear to be insufficient to model micro-multileaf collimators that have tri-faceted leaf ends and complex leaf profiles. This note indicates, however, that accurate Monte Carlo simulations of radiotherapy beams defined by a complex collimation device can be completed using BEAMnrc's standard VARMLC component module.---------- Methods: That this simple collimator model can produce spatially and dosimetrically accurate micro-collimated fields is illustrated using comparisons with ion chamber and film measurements of the dose deposited by square and irregular fields incident on planar, homogeneous water phantoms.---------- Results: Monte Carlo dose calculations for on- and off-axis fields are shown to produce good agreement with experimental values, even upon close examination of the penumbrae.--------- Conclusions: The use of a VARMLC model of the micro-multileaf collimator, along with a commissioned model of the associated linear accelerator, is therefore recommended as an alternative to the development or use of in-house or third-party component modules for simulating stereotactic radiotherapy and radiosurgery treatments. Simulation parameters for the VARMLC model are provided which should allow other researchers to adapt and use this model to study clinical stereotactic radiotherapy treatments.

Crystallographic characterization of the first reported crystalline form of the potent hallucinogen (R)-2-amino-1-(8-bromobenzo[1,2-b;5,4-b']difuran-4-yl)propane or `bromodragonfly': the 1:1 anhydrous proton-transfer compound with 3,5-dinitrosalicylic acid

The 1:1 proton-transfer compound of the potent substituted amphetamine hallucinogen (R)-1-(8-bromobenzo[1,2-b; 4,5-b']difuran-4-yl)-2-aminopropane (common trivial name 'bromodragonfly') with 3,5-dinitrosalicylic acid, 1-(8-bromobenzo[1,2-b;4,5-b']difuran-4-yl)-2-mmoniopropane 2-carboxy-4,6-dinitrophenolate, C13H13BrNO2+ C7H3N2O7- forms hydrogen-bonded cation-anion chain substructures comprising undulating head-to-tail anion chains formed through C(8) carboxyl O-H...O(nitro) associations and incorporating the aminium groups of the cations. The intra-chain cation-anion hydrogen-bonding associations feature proximal cyclic R33(8) interactions involving both a N+-H...O(phenolate) and the carboxyl O--H...O(nitro)associations. Also present are aromatic pi-pi ring interactions [minimum ring centroid separation, 3.566(2)A; inter-plane dihedral angle, 5.13(1)deg]. A lateral hydrogen-bonding interaction between the third aminium proton and a carboxyl O acceptor link the chain substructures giving a two-dimensional sheet structure. This determination represents the first of any form of this compound and confirms that it has the (R) absolute configuration. The atypical crystal stability is attributed both to the hydrogen-bonded chain substructures provided by the anions, which accommodate the aminium proton-donor groups of the cations and give cross-linking, and to the presence of cation--anion aromatic ring pi-pi interactions.

Desorption of stearic acid upon surfactant adsorbed montmorillonite : a thermogravimetric study

Thermal analysis and differential thermal analysis offers a means of studying the desorption of acids such as stearic acid from clay surfaces. Both adsorption and chemisorption can be distinguished through the differences in the temperature of the mass losses. Increased adsorption is achievable by adsorbing onto a surfactant adsorbed montmorillonite. Stearic acid sublimes at 179 °C but when adsorbed upon montmorillonite sublimes at 207 and 248 °C. These mass loss steps are ascribed to the desorption of the stearic acid on the external surfaces of the organoclays and from the de-chemisorption from the surfactant held in the interlayer of the montmorillonite.

Integrated Bayesian network frameworks for modelling complex ecological issues

Ecological problems are typically multi faceted and need to be addressed from a scientific and a management perspective. There is a wealth of modelling and simulation software available, each designed to address a particular aspect of the issue of concern. Choosing the appropriate tool, making sense of the disparate outputs, and taking decisions when little or no empirical data is available, are everyday challenges facing the ecologist and environmental manager. Bayesian Networks provide a statistical modelling framework that enables analysis and integration of information in its own right as well as integration of a variety of models addressing different aspects of a common overall problem. There has been increased interest in the use of BNs to model environmental systems and issues of concern. However, the development of more sophisticated BNs, utilising dynamic and object oriented (OO) features, is still at the frontier of ecological research. Such features are particularly appealing in an ecological context, since the underlying facts are often spatial and temporal in nature. This thesis focuses on an integrated BN approach which facilitates OO modelling. Our research devises a new heuristic method, the Iterative Bayesian Network Development Cycle (IBNDC), for the development of BN models within a multi-field and multi-expert context. Expert elicitation is a popular method used to quantify BNs when data is sparse, but expert knowledge is abundant. The resulting BNs need to be substantiated and validated taking this uncertainty into account. Our research demonstrates the application of the IBNDC approach to support these aspects of BN modelling. The complex nature of environmental issues makes them ideal case studies for the proposed integrated approach to modelling. Moreover, they lend themselves to a series of integrated sub-networks describing different scientific components, combining scientific and management perspectives, or pooling similar contributions developed in different locations by different research groups. In southern Africa the two largest free-ranging cheetah (Acinonyx jubatus) populations are in Namibia and Botswana, where the majority of cheetahs are located outside protected areas. Consequently, cheetah conservation in these two countries is focussed primarily on the free-ranging populations as well as the mitigation of conflict between humans and cheetahs. In contrast, in neighbouring South Africa, the majority of cheetahs are found in fenced reserves. Nonetheless, conflict between humans and cheetahs remains an issue here. Conservation effort in South Africa is also focussed on managing the geographically isolated cheetah populations as one large meta-population. Relocation is one option among a suite of tools used to resolve human-cheetah conflict in southern Africa. Successfully relocating captured problem cheetahs, and maintaining a viable free-ranging cheetah population, are two environmental issues in cheetah conservation forming the first case study in this thesis. The second case study involves the initiation of blooms of Lyngbya majuscula, a blue-green algae, in Deception Bay, Australia. L. majuscula is a toxic algal bloom which has severe health, ecological and economic impacts on the community located in the vicinity of this algal bloom. Deception Bay is an important tourist destination with its proximity to Brisbane, Australia’s third largest city. Lyngbya is one of several algae considered to be a Harmful Algal Bloom (HAB). This group of algae includes other widespread blooms such as red tides. The occurrence of Lyngbya blooms is not a local phenomenon, but blooms of this toxic weed occur in coastal waters worldwide. With the increase in frequency and extent of these HAB blooms, it is important to gain a better understanding of the underlying factors contributing to the initiation and sustenance of these blooms. This knowledge will contribute to better management practices and the identification of those management actions which could prevent or diminish the severity of these blooms.

Complex modelling of open system design for sustainable architecture

This paper argues a model of complex system design for sustainable architecture within a framework of entropy evolution. The spectrum of sustainable architecture consists of the efficient use of energy and material resource in life-cycle of buildings, the active involvement of the occupants in micro-climate control within buildings, and the natural environmental context. The interactions of the parameters compose a complex system of sustainable architectural design, of which the conventional linear and fragmented design technologies are insufficient to indicate holistic and ongoing environmental performance. The complexity theory of dissipative structure states a microscopic formulation of open system evolution, which provides a system design framework for the evolution of building environmental performance towards an optimization of sustainability in architecture.

Near infrared spectroscopy of benzoic acid adsorbed on montmorillonite

The adsorption of benzoic acid on both sodium and calcium montmorillonites has been studied by near infrared spectroscopy complimented with infrared spectroscopy. Upon adsorption of benzoic acid additional near infrared bands are observed at 8665 cm-1 and assigned to an interaction of benzoic acid with the water of hydration. Upon adsorption of the benzoic acid on Na-Mt, the NIR bands are now observed at 5877, 5951, 6028 and 6128 cm-1 and are assigned to the overtone and combination bands of the CH fundamentals. Additional bands at 4074, 4205, 4654 and 4678 cm-1 are attributed to CH combination bands resulting from the adsorption of the benzoic acid. Benzoic acid is used as a model molecule for adsorption studies. The application of near infrared spectroscopy to the study of adsorption has the potential for the removal of acids from polluted aqueous systems.

Investigating users’ intuitive interaction with complex artefacts

This paper examines the role of intuition in the way that people operate unfamiliar devices. Intuition is a type of cognitive processing that is often non-conscious and utilises stored experiential knowledge. Intuitive interaction involves the use of knowledge gained from other products and/or experiences. Two initial experimental studies revealed that prior exposure to products employing similar features helped participants to complete set tasks more quickly and intuitively, and that familiar features were intuitively used more often than unfamiliar ones. A third experiment confirmed that performance is affected by a person's level of familiarity with similar technologies, and also revealed that appearance (shape, size and labelling of features) seems to be the variable that most affects time spent on a task and intuitive uses during that time. Age also seems to have an effect. These results and their implications are discussed.

Phenyl-ring disorder in the two-dimensional hydrogen-bonded structure of the 1:1 proton-transfer salt of the diazo-dye precursor 4-(phenyldiazenyl)aniline (aniline yellow) with L-tartaric acid

The structure of the 1:1 proton-transfer compound from the reaction of L-tartaric acid with the azo-dye precursor aniline yellow [4-(phenylazo)aniline], 4-(phenyldiazenyl)anilinium hydrogen 2R,3R-tartrate C12H12N3+ . C4H6O6- has been determined at 200 K. The asymmetric unit of the compound contains two independent phenylazoanilinium cations and two hydrogen L-tartrate anions. The structure is unusual in that all four phenyl rings of both cations have identical 50% rotational disorder. The two hydrogen L-tartrate anions form independent but similar chains through head-to-tail carboxylic O--H...O~carboxyl~ hydrogen bonds [graph set C7] which are then extended into a two-dimensional hydrogen-bonded sheet structure through hydroxyl O--H...O hydrogen-bonding links. The anilinium groups of the phenyldiazenyl cations are incorporated into the sheets and also provide internal hydrogen-bonding extensions while their aromatic tails layer in the structure without significant interaction except for weak \p--\p interactions [minimum ring centroid separation, 3.844(3) \%A]. The hydrogen L-tartrate residues of both anions have the common short intramolecular hydroxyl O--H...O~carboxyl~ hydogen bonds. This work has provided a solution to the unusual disorder problem inherent in the structure of this salt as well as giving another example of the utility of the hydrogen tartrate in the generation of sheet substructures in molecular assembly processes.

Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine

The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

Effect of poly(acrylic acid) end-group functionality on inhibition of calcium oxalate crystal growth

A number of series of poly(acrylic acids) (PAA) of differing end-groups and molecular weights prepared using atom transfer radical polymerization were used as inhibitors for the crystallization of calcium oxalate at 23 and 80°C. As measured by turbidimetry and conductivity and as expected from previous reports, all PAA series were most effective for inhibition of crystallization at molecular weights of 1500–4000. However, the extent of inhibition was in general strongly dependent on the hydrophobicity and molecular weight of the end-group. These results may be explicable in terms of adsorption/desorption of PAA to growth sites on crystallites. The overall effectiveness of the series didn't follow a simple trend with end-group hydrophobicity, suggesting self-assembly behavior or a balance between adsorption and desorption rates to crystallite surfaces may be critical in the mechanism of inhibition of calcium oxalate crystallization.