The loss of carbon dioxide from activated perbenzoate anions in the gas phase : Unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.

Ion-molecule reactions of O,S-Dimethyl methylphosphonothioate : Evidence for intramolecular sulfur oxidation during VX perhydrolysis

The alkaline perhydrolysis of the nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) was investigated by studying the ion-molecule reactions of HOO(-) with O,S-dimethyl methylphosphonothioate in a modified linear ion-trap mass spectrometer. In addition to simple proton transfer, two other abundant product ions are observed at m/z 125 and 109 corresponding to the S-methyl methylphosphonothioate and methyl methylphosphonate anions, respectively. The structure of these product ions is demonstrated by a combination of collision-induced dissociation and isotope-labeling experiments that also provide evidence for their formation by nucleophilic reaction pathways, namely, (i) S(N)2 at carbon to yield the S-methyl methylphosphonothioate anion and (ii) nucleophilic addition at phosphorus affording a reactive pentavalent intermediate that readily undergoes internal sulfur oxidation and concomitant elimination of CH(3)SOH to yield the methyl methylphosphonate anion. Consistent with previous Solution phase observations of VX perhydrolysis, the toxic P-O cleavage product is not observed in this VX model system and theoretical calculations identify P-O cleavage to be energetically uncompetitive. Conversely, intramolecular sulfur oxidation is calculated to be extremely exothermic and kinetically accessible explaining its competitiveness with the facile gas phase proton transfer process. Elimination of a sulfur moiety deactivates the nerve agent VX and thus the intramolecular sulfur oxidation process reported here is also able to explain the selective perhydrolysis of the nerve agent to relatively nontoxic products.

Assessment of driving-related performance in chronic whiplash using an advanced driving simulator

Driving is often nominated as problematic by individuals with chronic whiplash associated disorders (WAD), yet driving-related performance has not been evaluated objectively. The purpose of this study was to test driving-related performance in persons with chronic WAD against healthy controls of similar age, gender and driving experience to determine if driving-related performance in the WAD group was sufficiently impaired to recommend fitness to drive assessment. Driving-related performance was assessed using an advanced driving simulator during three driving scenarios; freeway, residential and a central business district (CBD). Total driving duration was approximately 15 min. Five driving tasks which could cause a collision (critical events) were included in the scenarios. In addition, the effect of divided attention (identify red dots projected onto side or rear view mirrors) was assessed three times in each scenario. Driving performance was measured using the simulator performance index (SPI) which is calculated from 12 measures. z-Scores for all SPI measures were calculated for each WAD subject based on mean values of the control subjects. The z-scores were then averaged for the WAD group. A z-score of ≤−2 indicated a driving failing grade in the simulator. The number of collisions over the five critical events was compared between the WAD and control groups as was reaction time and missed response ratio in identifying the red dots. Seventeen WAD and 26 control subjects commenced the driving assessment. Demographic data were comparable between the groups. All subjects completed the freeway scenario but four withdrew during the residential and eight during the CBD scenario because of motion sickness. All scenarios were completed by 14 WAD and 17 control subjects. Mean z-scores for the SPI over the three scenarios was statistically lower in the WAD group (−0.3 ± 0.3; P < 0.05) but the score was not below the cut-off point for safe driving. There were no differences in the reaction time and missed response ratio in divided attention tasks between the groups (All P > 0.05). Assessment of driving in an advanced driving simulator for approximately 15 min revealed that driving-related performance in chronic WAD was not sufficiently impaired to recommend the need for fitness to drive assessment.

In-vehicle railway level crossing warning systems : can intelligent transport systems deliver?

Intelligent Transport System (ITS) technology is seen as a cost-effective way to increase the conspicuity of approaching trains and the effectiveness of train warnings at level crossings by providing an in-vehicle warning of an approaching train. The technology is often seen as a potential low-cost alternative to upgrading passive level crossings with traditional active warning systems (flashing lights and boom barriers). ITS platforms provide sensor, localization and dedicated short-range communication (DSRC) technologies to support cooperative applications such as collision avoidance for road vehicles. In recent years, in-vehicle warning systems based on ITS technology have been trialed at numerous locations around Australia, at level crossing sites with active and passive controls. While significant research has been conducted on the benefits of the technology in nominal operating modes, little research has focused on the effects of the failure modes, the human factors implications of unreliable warnings and the technology adoption process from the railway industry’s perspective. Many ITS technology suppliers originate from the road industry and often have limited awareness of the safety assurance requirements, operational requirements and legal obligations of railway operators. This paper aims to raise awareness of these issues and start a discussion on how such technology could be adopted. This paper will describe several ITS implementation cenarios and discuss failure modes, human factors considerations and the impact these scenarios are likely to have in terms of safety, railway safety assurance requirements and the practicability of meeting these requirements. The paper will identify the key obstacles impeding the adoption of ITS systems for the different implementation scenarios and a possible path forward towards the adoption of ITS technology.

Cryptanalysis of FORK-256

In this paper we present a cryptanalysis of a new 256-bit hash function, FORK-256, proposed by Hong et al. at FSE 2006. This cryptanalysis is based on some unexpected differentials existing for the step transformation. We show their possible uses in different attack scenarios by giving a 1-bit (resp. 2-bit) near collision attack against the full compression function of FORK-256 running with complexity of 2^125 (resp. 2^120) and with negligible memory, and by exhibiting a 22-bit near pseudo-collision. We also show that we can find collisions for the full compression function with a small amount of memory with complexity not exceeding 2^126.6 hash evaluations. We further show how to reduce this complexity to 2^109.6 hash computations by using 273 memory words. Finally, we show that this attack can be extended with no additional cost to find collisions for the full hash function, i.e. with the predefined IV.

Extending FORK-256 attack to the full hash function

In a paper published in FSE 2007, a way of obtaining near-collisions and in theory also collisions for the FORK-256 hash function was presented [8]. The paper contained examples of near-collisions for the compression function, but in practice the attack could not be extended to the full function due to large memory requirements and computation time. In this paper we improve the attack and show that it is possible to find near-collisions in practice for any given value of IV. In particular, this means that the full hash function with the prespecified IV is vulnerable in practice, not just in theory. We exhibit an example near-collision for the complete hash function.

Higher order universal one-way hash functions from the subset sum assumption

Universal One-Way Hash Functions (UOWHFs) may be used in place of collision-resistant functions in many public-key cryptographic applications. At Asiacrypt 2004, Hong, Preneel and Lee introduced the stronger security notion of higher order UOWHFs to allow construction of long-input UOWHFs using the Merkle-Damgård domain extender. However, they did not provide any provably secure constructions for higher order UOWHFs. We show that the subset sum hash function is a kth order Universal One-Way Hash Function (hashing n bits to m < n bits) under the Subset Sum assumption for k = O(log m). Therefore we strengthen a previous result of Impagliazzo and Naor, who showed that the subset sum hash function is a UOWHF under the Subset Sum assumption. We believe our result is of theoretical interest; as far as we are aware, it is the first example of a natural and computationally efficient UOWHF which is also a provably secure higher order UOWHF under the same well-known cryptographic assumption, whereas this assumption does not seem sufficient to prove its collision-resistance. A consequence of our result is that one can apply the Merkle-Damgård extender to the subset sum compression function with ‘extension factor’ k+1, while losing (at most) about k bits of UOWHF security relative to the UOWHF security of the compression function. The method also leads to a saving of up to m log(k+1) bits in key length relative to the Shoup XOR-Mask domain extender applied to the subset sum compression function.

Crystalline Si nanoparticles below crystallization threshold : effects of collisional heating in non-thermal atmospheric-pressure microplasmas

Nucleation and growth of highly crystalline silicon nanoparticles in atmospheric-pressure low-temperature microplasmas at gas temperatures well below the Si crystallization threshold and within a short (100 μs) period of time are demonstrated and explained. The modeling reveals that collision-enhanced ion fluxes can effectively increase the heat flux on the nanoparticle surface and this heating is controlled by the ion density. It is shown that nanoparticles can be heated to temperatures above the crystallization threshold. These combined experimental and theoretical results confirm the effective heating and structure control of Si nanoparticles at atmospheric pressure and low gas temperatures.

The effect of near-sheath dusts on a surface-wave-sustained gas discharge

The effect of near-sheath dusts on the rf power loss in a surface-wave-sustained gas discharge is studied. The planar plasma is bounded by a dielectric and consists of an inhomogeneous near-wall transition layer (sheath), a dusty plasma layer and an outer dust-free plasma. The discharge is maintained by high-frequency axially symmetrical surface waves. The surface-wave power loss from the most relevant dissipative mechanisms in typical discharge plasmas is analysed.

On the realization of the current-driven dust ion-acoustic instability

The current-driven dust ion-acoustic instability in a collisional dusty plasma is studied. The effects of dust-charge variation, electron and ion capture by the dust grains, as well as various dissipative mechanisms leading to the changes of the particles momenta, are taken into account. It is shown that the threshold for the excitation of the dust ion-acoustic waves can be high because of the large dissipation rate induced by the dusts. © 1999 American Institute of Physics.

Self-interaction of high-frequency surface waves in magnetoactive plasma planar waveguide

The nonlinear effect of hf surface waves self-interaction in a magnetoactive planar plasma waveguide is studies. The waveguide structure under consideration can be formed by gaseous or semiconducting homogeneous plasma, which is limited by a perfectly conducting metal surface. The surface (localized near the surface) wave perturbations propagating on the plasma-metal boundary perpendicular to the constant external magnetic field, are investigated. The nonlinear frequency shift connected with interaction of the second harmonic and static surface perturbations with the main frequency wave, is determined using the approximation of weak nonlinearity. It is shown that the process of double-frequency signal generation is the dissipative one as a result of bulk wave excitation on the surface wave second harmonic.

New constructions of anonymous membership broadcasting schemes

An anonymous membership broadcast scheme is a method in which a sender broadcasts the secret identity of one out of a set of n receivers, in such a way that only the right receiver knows that he is the intended receiver, while the others can not determine any information about this identity (except that they know that they are not the intended ones). In a w-anonymous membership broadcast scheme no coalition of up to w receivers, not containing the selected receiver, is able to determine any information about the identity of the selected receiver. We present two new constructions of w-anonymous membership broadcast schemes. The first construction is based on error-correcting codes and we show that there exist schemes that allow a flexible choice of w while keeping the complexities for broadcast communication, user storage and required randomness polynomial in log n,. The second construction is based on the concept of collision-free arrays, which is introduced in this paper. The construction results in more flexible schemes, allowing trade-offs between different complexities.

RPAS integration within an Australian ATM system : what equipment and which airspace

The Australian Civil Aviation Safety Authority (CASA) currently lists more than 100 separate entities or organisations which maintain a UAS Operator Certificate (UOC) [1]. Approved operations are overwhelmingly a permutation of aerial photography, surveillance, survey or spotting and predominantly, are restricted to Visual Line of Sight (VLOS) operations, below 400 feet, and not within 3 NM of an aerodrome. However, demand is increasing for a Remote Piloted Aerial System (RPAS) regulatory regime which facilitates more expansive operations, in particular unsegregated, Beyond Visual Line of Sight (BVLOS) operations. Despite this demand, there is national and international apprehension regarding the necessary levels of airworthiness and operational regulation required to maintain safety and minimise the risk associated with unsegregated operations. Fundamental to addressing these legitimate concerns will be the mechanisms that underpin safe separation and collision avoidance. Whilst a large body of research has been dedicated to investigating on-board, Sense and Avoid (SAA) technology necessary to meet this challenge, this paper focuses on the contribution of the NAS to separation assurance, and how it will support, as well as complicate RPAS integration. The paper collates and presents key, but historically disparate, threads of Australian RPAS and NAS related information, and distils it with a filter focused on minimising RPAS collision risk. Our ongoing effort is motivated by the need to better understand the separation assurance contribution provided by the NAS layers, in the first instance, and subsequently employ this information to identify scenarios where the coincident collision risk is demonstrably low, providing legitimate substantiation for concessions on equipage and airworthiness standards.

Evaluation of emerging intelligent transport systems to improve safety on level crossings : an overview

Safety at railway level crossings (RLX) is one part of a wider picture of safety within the whole transport system. Governments, the rail industry and road organisations have used a variety of countermeasures for many years to improve RLX safety. New types of interventions are required in order to reduce the number of crashes and associated social costs at railway crossings. This paper presents the results of a large research program which aimed to assess the effectiveness of emerging Intelligent Transport Systems (ITS) interventions, both on-road and in-vehicle based, to improve the safety of car drivers at RLXs in Australia. The three most promising technologies selected from the literature review and focus groups were tested in an advanced driving simulator to provide a detailed assessment of their effects on driver behaviour. The three interventions were: (i) in-vehicle visual warning using a GPS/smartphone navigation-like system, (ii) in-vehicle audio warning and; (iii) on-road intervention known as valet system (warning lights on the road surface activated as a train approaches). The effects of these technologies on 57 participants were assessed in a systematic approach focusing on the safety of the intervention, effects on the road traffic around the crossings and driver’s acceptance of the technology. Given that the ITS interventions were likely to provide a benefit by improving the driver’s awareness of the crossing status in low visibility conditions, such conditions were investigated through curves in the track before arriving at the crossing. ITS interventions were also expected to improve driver behaviour at crossings with high traffic (blocking back issue), which were also investigated at active crossings. The key findings are: (i) interventions at passive crossings are likely to provide safety benefits; (ii) the benefits of ITS interventions on driver behaviour at active crossings are limited; (iii) the trialled ITS interventions did not show any issues in terms of driver distraction, driver acceptance or traffic delays; (iv) these interventions are easy to use, do not increase driver workload substantially; (v) participants’ intention to use the technology is high and; (vi) participants saw most value in succinct messages about approaching trains as opposed to knowing the RLX locations or the imminence of a collision with a train.

A runtime integrity monitoring framework for real-time relative positioning systems based on GPS and DSRC

This paper provides a three-layered framework to monitor the positioning performance requirements of Real-time Relative Positioning (RRP) systems of the Cooperative Intelligent Transport Systems (C-ITS) that support Cooperative Collision Warning (CCW) applications. These applications exploit state data of surrounding vehicles obtained solely from the Global Positioning System (GPS) and Dedicated Short-Range Communications (DSRC) units without using other sensors. To this end, the paper argues the need for the GPS/DSRC-based RRP systems to have an autonomous monitoring mechanism, since the operation of CCW applications is meant to augment safety on roads. The advantages of autonomous integrity monitoring are essential and integral to any safety-of-life system. The autonomous integrity monitoring framework proposed necessitates the RRP systems to detect/predict the unavailability of their sub-systems and of the integrity monitoring module itself, and, if available, to account for effects of data link delays and breakages of DSRC links, as well as of faulty measurement sources of GPS and/or integrated augmentation positioning systems, before the information used for safety warnings/alarms becomes unavailable, unreliable, inaccurate or misleading. Hence, a monitoring framework using a tight integration and correlation approach is proposed for instantaneous reliability assessment of the RRP systems. Ultimately, using the proposed framework, the RRP systems will provide timely alerts to users when the RRP solutions cannot be trusted or used for the intended operation.