Hydrogen bonding in the water stabilized structure of the modified unsymmetrically substituted viologen chromophore, N-ethyl-N'-(2-phosphonomethyl)-4,4'-bipyridylium dichloride

The crystal structure of the modified unsymmetrically N, N'-substituted viologen chromophore, N-ethyl- N'-(2-phosphonoethyl)-4, 4'-bipyridinium dichloride 0.75 hydrate. (1) has been determined. Crystals are triclinic, space group P-1 with Z = 2 in a cell with a = 7.2550(1), b = 13.2038(5), c = 18.5752(7) Å, α = 86.495(3), β = 83.527(2), γ = 88.921(2)o. The two independent but pseudo-symmetrically related cations in the asymmetric unit form one-dimensional hydrogen-bonded chains through short homomeric phosphonic acid O-H...O links [2.455(4), 2.464(4)A] while two of the chloride anions are similarly strongly linked to phosphonic acid groups [O-H…Cl, 2.889(4), 2.896(4)Å]. The other two chloride anions together with the two water molecules of solvation (one with partial occupancy) form unusual cyclic hydrogen-bonded bis(Cl...water) dianion units which lie between the layers of bipyridylium rings of the cation chain structures with which they are weakly associated.

The knowledge exchange intermediary as service provider : a discussion and an Australian case

The critical impact of innovation on national and the global economies has been discussed at length in the literature. Economic development requires the diffusion of innovations into markets. It has long been recognised that economic growth and development depends upon a constant stream of innovations. Governments have been keenly aware of the need to ensure this flow does not dry to a trickle and have introduced many and varied industry policies and interventions to assist in seeding, supporting and diffusing innovations. In Australia, as in many countries, Government support for the transfer of knowledge especially from publicly funded research has resulted in the creation of knowledge exchange intermediaries. These intermediaries are themselves service organisations, seeking innovative service offerings for their markets. The choice for most intermediaries is generally a dichotomous one, between market-pull and technology-push knowledge exchange programmes. In this article, we undertake a case analysis of one such innovative intermediary and its flagship programme. We then compare this case with other successful intermediaries in Europe. We put forward a research proposition that the design of intermediary programmes must match the service type they offer. That is, market-pull programmes require market-pull design, in close collaboration with industry, whereas technology programmes can be problem-solving innovations where demand is latent. The discussion reflects the need for an evolution in knowledge transfer policies and programmes beyond the first generation ushered in with the US Bayh-Dole Act (1980) and Stevenson-Wydler Act (1984). The data analysed is a case study comparison of market-pull and technology-push programmes, focusing on primary and secondary socio-economic benefits (using both Australian and international comparisons).

One-time-password-authenticated key exchange

To reduce the damage of phishing and spyware attacks, banks, governments, and other security-sensitive industries are deploying one-time password systems, where users have many passwords and use each password only once. If a single password is compromised, it can be only be used to impersonate the user once, limiting the damage caused. However, existing practical approaches to one-time passwords have been susceptible to sophisticated phishing attacks. ---------- We give a formal security treatment of this important practical problem. We consider the use of one-time passwords in the context of password-authenticated key exchange (PAKE), which allows for mutual authentication, session key agreement, and resistance to phishing attacks. We describe a security model for the use of one-time passwords, explicitly considering the compromise of past (and future) one-time passwords, and show a general technique for building a secure one-time-PAKE protocol from any secure PAKE protocol. Our techniques also allow for the secure use of pseudorandomly generated and time-dependent passwords.

Predicate-based key exchange

We provide the first description of and security model for authenticated key exchange protocols with predicate-based authentication. In addition to the standard goal of session key security, our security model also provides for credential privacy: a participating party learns nothing more about the other party's credentials than whether they satisfy the given predicate. Our model also encompasses attribute-based key exchange since it is a special case of predicate-based key exchange.---------- We demonstrate how to realize a secure predicate-based key exchange protocol by combining any secure predicate-based signature scheme with the basic Diffie-Hellman key exchange protocol, providing an efficient and simple solution.

Hydrate stabilization in the three-dimensional hydrogen-bonded structure of the brucinium compound, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate

The crystal structure of the 2:1 proton-transfer compound of brucine with biphenyl-4,4’-disulfonate, bis(2,3-dimethoxy-10-oxostrychnidinium) biphenyl-4,4'-disulfonate hexahydrate (1) has been determined at 173 K. Crystals are monoclinic, space group P21 with Z = 2 in a cell with a = 8.0314(2), b = 29.3062(9), c = 12.2625(3) Å, β = 101.331(2)o. The crystallographic asymmetric unit comprises two brucinium cations, a biphenyl-4,4'-disulfonate dianion and six water molecules of solvation. The brucinium cations form a variant of the common undulating and overlapping head-to-tail sheet sub-structure. The sulfonate dianions are also linked head-to-tail by hydrogen bonds into parallel zig-zag chains through clusters of six water molecules of which five are inter-associated, featuring conjoint cyclic eight-membered hydrogen-bonded rings [graph sets R33(8) and R34(8)], comprising four of the water molecules and closed by sulfonate O-acceptors. These chain structures occupy the cavities between the brucinium cation sheets and are linked to them peripherally through both brucine N+-H...Osulfonate and Ocarbonyl…H-Owater to sulfonate O bridging hydrogen bonds, forming an overall three-dimensional framework structure. This structure determination confirms the importance of water in the stabilization of certain brucine compounds which have inherent crystal instability.

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.

Structure of selected basic copper (II) sulphate minerals based upon spectroscopy : implications for hydrogen bonding

The application of near-infrared and infrared spectroscopy has been used for identification and distinction of basic Cu-sulphates that include devilline, chalcoalumite and caledonite. Near-infrared spectra of copper sulphate minerals confirm copper in divalent state. Jahn-Teller effect is more significant in chalcoalumite where 2B1g ® 2B2g transition band shows a larger splitting (490 cm-1) confirming more distorted octahedral coordination of Cu2+ ion. One symmetrical band at 5145 cm-1 with shoulder band 5715 cm-1 result from the absorbed molecular water in the copper complexes are the combinations of OH vibrations of H2O. One sharp band at around 3400 cm-1 in IR common to the three complexes is evidenced by Cu-OH vibrations. The strong absorptions observed at 1685 and 1620 cm-1 for water bending modes in two species confirm strong hydrogen bonding in devilline and chalcoalumite. The multiple bands in v3 and v4(SO4)2- stretching regions are attributed to the reduction of symmetry to the sulphate ion from Td to C2V. Chalcoalumite, the excellent IR absorber over the range 3800-500 cm-1 is treated as most efficient heat insulator among the Cu-sulphate complexes.

A hydrogen tethered inhibitor of matrix metalloproteinases

During wound repair, the balance between matrix metalloproteinases (MMPs) and their natural inhibitors (the TIMPs) is crucial for the normal extra cellular matrix turnover. However, the over expression of several MMPs including MMP-1, 2, 3, 8, 9 and MMP-10, combined with abnormally high levels of activation or low expression of TIMPs, may contribute to excessive degradation of connective tissue and formation of chronic ulcers. There are many groups exploring strategies for promoting wound healing involving delivery of growth factors, cells, ECM components and small molecules. Our approach for improving the balance of MMPs is not to add anything more to the wound, but instead to neutralise the over-expressed MMPs using inhibitors tethered to a bandage-like hydrogel. Our in vitro experiments using designed synthetic pseudo peptide inhibitors have been demonstrated to inhibit MMP activity in standard solutions. These inhibitors have also been tethered to polyethylene glycol hydrogels using a facile reaction between the linker unit on the inhibitor and the gel. After tethering the inhibition of MMPs diminishes to some extent and we postulate that this arises due to poor diffusion of the MMPs into the gels. When the tethered inhibitors were tested against chronic wound fluid obtained against patients we observed over 40% inhibition in proteolytic activity suggesting our approach may prove useful in rebalancing MMPs within chronic wounds.

Spectroscopy of selected copper group minerals : chalcophyllite and chenevixite-implications for hydrogen bonding

NIR and IR spectroscopy has been applied for detection of chemical species and the nature of hydrogen bonding in arsenate complexes. The structure and spectral properties of copper(II) arsenate minerals chalcophyllite and chenevixite are compared with copper(II) sulphate minerals devilline, chalcoalumite and caledonite. Split NIR bands in the electronic spectrum of two ranges 11700-8500 cm-1 and 8500-7200 cm-1 confirm distortion of octahedral symmetry for Cu(II) in the arsenate complexes. The observed bands with maxima at 9860 and 7750 cm-1 are assigned to Cu(II) transitions 2B1g ® 2B2g and 2B1g ® 2A1g. Overlapping bands in the NIR region 4500-4000 cm-1 is the effect of multi anions OH-, (AsO4)3- and (SO4)2-. The observation of broad and diffuse bands in the range 3700-2900 cm-1 confirms strong hydrogen bonding in chalcophyllite relative to chenevixite. The position of the water bending vibrations indicates the water is strongly hydrogen bonded in the mineral structure. The strong absorption feature centred at 1644 cm-1 in chalcophyllite indicates water is strongly hydrogen bonded in the mineral structure. The H2O-bending vibrations shift to low wavenumbers in chenevixite and an additional band observed at 1390 cm-1 is related to carbonate impurity. The characterisation of IR spectra by ν3 antisymmetric stretching vibrations of (SO4)2- and (AsO4)3 ions near 1100 and 800 cm-1 respectively is the result of isomorphic substitution for arsenate by sulphate in both the minerals of chalcophyllite and chenevixite.

Attribute-based authenticated key exchange

We introduce the concept of attribute-based authenticated key exchange (AB-AKE) within the framework of ciphertext policy attribute-based systems. A notion of AKE-security for AB-AKE is presented based on the security models for group key exchange protocols and also taking into account the security requirements generally considered in the ciphertext policy attribute-based setting. We also extend the paradigm of hybrid encryption to the ciphertext policy attribute-based encryption schemes. A new primitive called encapsulation policy attribute-based key encapsulation mechanism (EP-AB-KEM) is introduced and a notion of chosen ciphertext security is de�ned for EP-AB-KEMs. We propose an EP-AB-KEM from an existing attribute-based encryption scheme and show that it achieves chosen ciphertext security in the generic group and random oracle models. We present a generic one-round AB-AKE protocol that satis�es our AKE-security notion. The protocol is generically constructed from any EP-AB-KEM that satis�es chosen ciphertext security. Instantiating the generic AB-AKE protocol with our EP-AB-KEM will result in a concrete one-round AB-AKE protocol also secure in the generic group and random oracle models.

Generic one round group key exchange in the standard model

Minimizing complexity of group key exchange (GKE) protocols is an important milestone towards their practical deployment. An interesting approach to achieve this goal is to simplify the design of GKE protocols by using generic building blocks. In this paper we investigate the possibility of founding GKE protocols based on a primitive called multi key encapsulation mechanism (mKEM) and describe advantages and limitations of this approach. In particular, we show how to design a one-round GKE protocol which satisfies the classical requirement of authenticated key exchange (AKE) security, yet without forward secrecy. As a result, we obtain the first one-round GKE protocol secure in the standard model. We also conduct our analysis using recent formal models that take into account both outsider and insider attacks as well as the notion of key compromise impersonation resilience (KCIR). In contrast to previous models we show how to model both outsider and insider KCIR within the definition of mutual authentication. Our analysis additionally implies that the insider security compiler by Katz and Shin from ACM CCS 2005 can be used to achieve more than what is shown in the original work, namely both outsider and insider KCIR.

Urban rural water exchange : PRW in the Lockyer Valley

A significant amount (ca. 15-25 GL/a) of PRW (Purified Recycled Water) from urban areas is foreseen as augmentation of the depleted groundwater resources of the Lockyer Valley (approx. 80 km west of Brisbane). Theresearch project uses field investigations, lab trials and modelling techniques to address the key challenges: (i) how to determine benefits of individual users from the augmentation of a natural common pool resource; (ii) how to minimise impacts of applying different quality water on the Lockyer soils, to creeks and on aquifier materials; (iii) how to minimuse mobilisation of salts in the unsaturated and saturated zones as a result of increased deep drainage; (iv) determination of potential for direct aquifer recharge using injection wells?

Design and analysis of group key exchange protocols

A group key exchange (GKE) protocol allows a set of parties to agree upon a common secret session key over a public network. In this thesis, we focus on designing efficient GKE protocols using public key techniques and appropriately revising security models for GKE protocols. For the purpose of modelling and analysing the security of GKE protocols we apply the widely accepted computational complexity approach. The contributions of the thesis to the area of GKE protocols are manifold. We propose the first GKE protocol that requires only one round of communication and is proven secure in the standard model. Our protocol is generically constructed from a key encapsulation mechanism (KEM). We also suggest an efficient KEM from the literature, which satisfies the underlying security notion, to instantiate the generic protocol. We then concentrate on enhancing the security of one-round GKE protocols. A new model of security for forward secure GKE protocols is introduced and a generic one-round GKE protocol with forward security is then presented. The security of this protocol is also proven in the standard model. We also propose an efficient forward secure encryption scheme that can be used to instantiate the generic GKE protocol. Our next contributions are to the security models of GKE protocols. We observe that the analysis of GKE protocols has not been as extensive as that of two-party key exchange protocols. Particularly, the security attribute of key compromise impersonation (KCI) resilience has so far been ignored for GKE protocols. We model the security of GKE protocols addressing KCI attacks by both outsider and insider adversaries. We then show that a few existing protocols are not secure against KCI attacks. A new proof of security for an existing GKE protocol is given under the revised model assuming random oracles. Subsequently, we treat the security of GKE protocols in the universal composability (UC) framework. We present a new UC ideal functionality for GKE protocols capturing the security attribute of contributiveness. An existing protocol with minor revisions is then shown to realize our functionality in the random oracle model. Finally, we explore the possibility of constructing GKE protocols in the attribute-based setting. We introduce the concept of attribute-based group key exchange (AB-GKE). A security model for AB-GKE and a one-round AB-GKE protocol satisfying our security notion are presented. The protocol is generically constructed from a new cryptographic primitive called encapsulation policy attribute-based KEM (EP-AB-KEM), which we introduce in this thesis. We also present a new EP-AB-KEM with a proof of security assuming generic groups and random oracles. The EP-AB-KEM can be used to instantiate our generic AB-GKE protocol.