Hydrazine-hydrate intercalated halloysite under controlled-rate thermal analysis conditions

The thermal behaviour of halloysite fully expanded with hydrazine-hydrate has been investigated in nitrogen atmosphere under dynamic heating and at a constant, pre-set decomposition rate of 0.15 mg min-1. Under controlled-rate thermal analysis (CRTA) conditions it was possible to resolve the closely overlapping decomposition stages and to distinguish between adsorbed and bonded reagent. Three types of bonded reagent could be identified. The loosely bonded reagent amounting to 0.20 mol hydrazine-hydrate per mol inner surface hydroxyl is connected to the internal and external surfaces of the expanded mineral and is present as a space filler between the sheets of the delaminated mineral. The strongly bonded (intercalated) hydrazine-hydrate is connected to the kaolinite inner surface OH groups by the formation of hydrogen bonds. Based on the thermoanalytical results two different types of bonded reagent could be distinguished in the complex. Type 1 reagent (approx. 0.06 mol hydrazine-hydrate/mol inner surface OH) is liberated between 77 and 103°C. Type 2 reagent is lost between 103 and 227°C, corresponding to a quantity of 0.36 mol hydrazine/mol inner surface OH. When heating the complex to 77°C under CRTA conditions a new reflection appears in the XRD pattern with a d-value of 9.6 Å, in addition to the 10.2 Ĺ reflection. This new reflection disappears in contact with moist air and the complex re-expands to the original d-value of 10.2 Å in a few h. The appearance of the 9.6 Å reflection is interpreted as the expansion of kaolinite with hydrazine alone, while the 10.2 Å one is due to expansion with hydrazine-hydrate. FTIR (DRIFT) spectroscopic results showed that the treated mineral after intercalation/deintercalation and heat treatment to 300°C is slightly more ordered than the original (untreated) clay.

Career development and personal functioning differences between work-bound and non-work bound students

We surveyed 506 Australian high school students on career development (exploration, planning, job-knowledge, decision-making, indecision), personal functioning (well-being, self-esteem, life satisfaction, school satisfaction) and control variables (parents’ education, school achievement), and tested differences among work-bound, college-bound and university-bound students. The work-bound students had the poorest career development and personal functioning, the university-bound students the highest, with the college-bound students falling in-between the other two groups. Work-bound students did poorest, even after controlling for parental education and school achievement. The results suggest a relationship between career development and personal functioning in high school students.

8-Ammonionaphthalene-2-sulfonate monohydrate : the zwitterionic hydrate of 1,7-Cleve's acid

The structure of 8-amino-2-naphthalenesulfonic acid monohydrate (1,7-Cleve's acid hydrate), C10H9NO3S.H2O, shows the presence of a sulfonate-aminium group zwitterion, both groups and the water molecule of solvation giving cyclic R3/3(8) intermolecular hydrogen-bonding interactions forming chains which extend down a axis of the unit cell. Additional peripheral associations, including weak aromatic ring pi-pi interactions [centroid-centroid distance 3.6299(15)A], result in a two-dimensional sheet structure.

Unusual hydrate stabilization in the two-dimensional layered structure of quinacrinium bis(2-carboxy-4,5-dichlorobenzoate) tetrahydrate, a proton-transfer compound of the drug quinacrine

The crystal structure of the hydrated proton-transfer compound of the drug quinacrine [rac-N'-(6-chloro-2-methoxyacridin-9-yl)-N,N-diethylpentane-1,4-diamine] with 4,5-dichlorophthalic acid, C23H32ClN3O2+ . 2(C8H3Cl2O4-).4H2O (I), has been determined at 200 K. The four labile water molecules of solvation form discrete ...O--H...O--H... hydrogen-bonded chains parallel to the quinacrine side chain, the two N--H groups of which act as hydrogen-bond donors for two of the water acceptor molecules. The other water molecules, as well as the acridinium H atom, also form hydrogen bonds with the two anion species and extend the structure into two-dimensional sheets. Between these sheets there are also weak cation--anion and anion--anion pi-pi aromatic ring interactions. This structure represents only the third example of a simple quinacrine derivative for which structural data are available but differs from the other two in that it is unstable in the X-ray beam due to efflorescence, probably associated with the destruction of the unusual four-membered water chain structures.

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.

Strengthening and formally verifying privacy in identity management systems

In a digital world, users’ Personally Identifiable Information (PII) is normally managed with a system called an Identity Management System (IMS). There are many types of IMSs. There are situations when two or more IMSs need to communicate with each other (such as when a service provider needs to obtain some identity information about a user from a trusted identity provider). There could be interoperability issues when communicating parties use different types of IMS. To facilitate interoperability between different IMSs, an Identity Meta System (IMetS) is normally used. An IMetS can, at least theoretically, join various types of IMSs to make them interoperable and give users the illusion that they are interacting with just one IMS. However, due to the complexity of an IMS, attempting to join various types of IMSs is a technically challenging task, let alone assessing how well an IMetS manages to integrate these IMSs. The first contribution of this thesis is the development of a generic IMS model called the Layered Identity Infrastructure Model (LIIM). Using this model, we develop a set of properties that an ideal IMetS should provide. This idealized form is then used as a benchmark to evaluate existing IMetSs. Different types of IMS provide varying levels of privacy protection support. Unfortunately, as observed by Jøsang et al (2007), there is insufficient privacy protection in many of the existing IMSs. In this thesis, we study and extend a type of privacy enhancing technology known as an Anonymous Credential System (ACS). In particular, we extend the ACS which is built on the cryptographic primitives proposed by Camenisch, Lysyanskaya, and Shoup. We call this system the Camenisch, Lysyanskaya, Shoup - Anonymous Credential System (CLS-ACS). The goal of CLS-ACS is to let users be as anonymous as possible. Unfortunately, CLS-ACS has problems, including (1) the concentration of power to a single entity - known as the Anonymity Revocation Manager (ARM) - who, if malicious, can trivially reveal a user’s PII (resulting in an illegal revocation of the user’s anonymity), and (2) poor performance due to the resource-intensive cryptographic operations required. The second and third contributions of this thesis are the proposal of two protocols that reduce the trust dependencies on the ARM during users’ anonymity revocation. Both protocols distribute trust from the ARM to a set of n referees (n > 1), resulting in a significant reduction of the probability of an anonymity revocation being performed illegally. The first protocol, called the User Centric Anonymity Revocation Protocol (UCARP), allows a user’s anonymity to be revoked in a user-centric manner (that is, the user is aware that his/her anonymity is about to be revoked). The second protocol, called the Anonymity Revocation Protocol with Re-encryption (ARPR), allows a user’s anonymity to be revoked by a service provider in an accountable manner (that is, there is a clear mechanism to determine which entity who can eventually learn - and possibly misuse - the identity of the user). The fourth contribution of this thesis is the proposal of a protocol called the Private Information Escrow bound to Multiple Conditions Protocol (PIEMCP). This protocol is designed to address the performance issue of CLS-ACS by applying the CLS-ACS in a federated single sign-on (FSSO) environment. Our analysis shows that PIEMCP can both reduce the amount of expensive modular exponentiation operations required and lower the risk of illegal revocation of users’ anonymity. Finally, the protocols proposed in this thesis are complex and need to be formally evaluated to ensure that their required security properties are satisfied. In this thesis, we use Coloured Petri nets (CPNs) and its corresponding state space analysis techniques. All of the protocols proposed in this thesis have been formally modeled and verified using these formal techniques. Therefore, the fifth contribution of this thesis is a demonstration of the applicability of CPN and its corresponding analysis techniques in modeling and verifying privacy enhancing protocols. To our knowledge, this is the first time that CPN has been comprehensively applied to model and verify privacy enhancing protocols. From our experience, we also propose several CPN modeling approaches, including complex cryptographic primitives (such as zero-knowledge proof protocol) modeling, attack parameterization, and others. The proposed approaches can be applied to other security protocols, not just privacy enhancing protocols.

Practical stability of approximating discrete-time filters with respect to model mismatch using relative entropy concepts

This paper establishes practical stability results for an important range of approximate discrete-time filtering problems involving mismatch between the true system and the approximating filter model. Using local consistency assumption, the practical stability established is in the sense of an asymptotic bound on the amount of bias introduced by the model approximation. Significantly, these practical stability results do not require the approximating model to be of the same model type as the true system. Our analysis applies to a wide range of estimation problems and justifies the common practice of approximating intractable infinite dimensional nonlinear filters by simpler computationally tractable filters.

Closing the gap between bandit and full-information online optimization : high-probability regret bound

We demonstrate a modification of the algorithm of Dani et al for the online linear optimization problem in the bandit setting, which allows us to achieve an O( \sqrt{T ln T} ) regret bound in high probability against an adaptive adversary, as opposed to the in expectation result against an oblivious adversary of Dani et al. We obtain the same dependence on the dimension as that exhibited by Dani et al. The results of this paper rest firmly on those of Dani et al and the remarkable technique of Auer et al for obtaining high-probability bounds via optimistic estimates. This paper answers an open question: it eliminates the gap between the high-probability bounds obtained in the full-information vs bandit settings.

Practical stability with respect to model mismatch of approximate discrete-time output feedback control

This paper establishes a practical stability result for discrete-time output feedback control involving mismatch between the exact system to be stabilised and the approximating system used to design the controller. The practical stability is in the sense of an asymptotic bound on the amount of error bias introduced by the model approximation, and is established using local consistency properties of the systems. Importantly, the practical stability established here does not require the approximating system to be of the same model type as the exact system. Examples are presented to illustrate the nature of our practical stability result.