Pt(II) bipyridyl complexes bearing substituted fluorenyl motif on the bipyridyl and acetylide ligands : synthesis, photophysics, and reverse saturable absorption

A series of Pt(II) diimine complexes bearing benzothiazolylfluorenyl (BTZ-F8), diphenylaminofluorenyl (NPh2- F8), or naphthalimidylfluorenyl (NI-F8) motifs on the bipyridyl or acetylide ligands (Pt-4−Pt-8), (i.e., {4,4′-bis[7-R1-F8-(≡)n-]bpy}Pt(7- R2-F8- ≡ -)2, where F8 = 9,9′-di(2-ethylhexyl)fluorene, bpy = 2,2′- bipyridine, Pt-4: R1 = R2 = BTZ, n = 0; Pt-5: R1 = BTZ, R2 = NI, n = 0; Pt-6: R1 = R2 = BTZ, n = 1; Pt-7: R1 = BTZ, R2 = NPh2, n = 1; Pt- 8: R1 = NPh2, R2 = BTZ, n = 1) were synthesized. Their ground-state and excited-state properties and reverse saturable absorption performances were systematically investigated. The influence of these motifs on the photophysics of the complexes was investigated by spectroscopic methods and simulated by time-dependent density functional theory (TDDFT). The intense absorption bands below 410 nm for these complexes is assigned to predominantly 1π,π* transitions localized on either the bipyridine or the acetylide ligands; while the broad low-energy absorption bands between 420 and 575 nm are attributed to essentially 1MLCT (metal-to-ligand charge transfer)/ 1LLCT (ligand-to-ligand charge transfer) transitions, likely mixed with some 1ILCT (intraligand charge transfer) transition for Pt-4−Pt-7, and predominantly 1ILCT transition admixing with minor 1MLCT/1LLCT characters for Pt-8. The different substituents on the acetylide and bipyridyl ligands, and the degrees of π-conjugation in the bipyridyl ligand influence both the 1π,π* and charge transfer transitions pronouncedly. All complexes are emissive at room temperature. Upon excitation at their respective absorption band maxima, Pt-4, Pt-6, and Pt-8 exhibit acetylide ligand localized 1π,π* fluorescence and 3MLCT/3LLCT phosphorescence in CH2Cl2, while Pt-5 manifests 1ILCT fluorescence and 3ILCT phosphorescence. However, only 1LLCT fluorescence was observed for Pt-7 at room temperature. The nanosecond transient absorption study was carried out for Pt-4−Pt-8 in CH3CN. Except for Pt-7 that contains NPh2 at the acetylide ligands, Pt-4−Pt-6 and Pt-8 all exhibit weak to moderate excited-state absorption in the visible spectral region. Reverse saturable absorption (RSA) of these complexes was demonstrated at 532 nm using 4.1 ns laser pulses in a 2 mm cuvette. The strength of RSA follows this trend: Pt-4 > Pt-5 > Pt-7 > Pt-6 > Pt-8. Incorporation of electron-donating substituent NPh2 on the bipyridyl ligand significantly decreases the RSA, while shorter π-conjugation in the bipyridyl ligand increases the RSA. Therefore, the substituent at either the acetylide ligands or the bipyridyl ligand could affect the singlet and triplet excited-state characteristics significantly, which strongly influences the RSA efficiency.

The influence of flight speed on the ranging performance of bats using frequency modulated echolocation pulses

Many species of bat use ultrasonic frequency modulated (FM) pulses to measure the distance to objects by timing the emission and reception of each pulse. Echolocation is mainly used in flight. Since the flight speed of bats often exceeds 1% of the speed of sound,Doppler effects will lead to compression of the time between emission and reception as well as an elevation of the echo frequencies, resulting in a distortion of the perceived range. This paper describes the consequences of these Doppler effects on the ranging performance of bats using different pulse designs. The consequences of Doppler effects on ranging performance described in this paper assume bats to have a very accurate ranging resolution, which is feasible with a filterbank receiver. By modeling two receiver types, it was first established that the effects of Doppler compression are virtually independent of the receiver type. Then, used a cross-correlation model was used to investigate the effect of flight speed on Doppler tolerance and range–Doppler coupling separately. This paper further shows how pulse duration, bandwidth, function type, and harmonics influence Doppler tolerance and range–Doppler coupling. The influence of each signal parameter is illustrated using calls of several bat species. It is argued that range–Doppler coupling is a significant source of error in bat echolocation, and various strategies bats could employ to deal with this problem, including the use of range rate information are discussed.

Defence relationship health - deployment impact experience. A prospective study of the impact of deployment on the intimate relationships of Australian Army personnel

A comprehensive literature review has been undertaken exploring the stressors placed on the personal relationships of Australian Army personnel, through service life and also overseas deployments. This work is the first step in a program of research aimed at developing a screening tool, aimed at acting as an early warning system to enable the right assistance to be given to affected personnel at the earliest possible time. It is envisioned that this tool will be utilised by the day-to-day managers of Australian Army personnel, of whom the vast majority are not health practitioners. This review has identified the commonalities of relationships that last through service life and/or deployments, and those that fail. These factors are those which will aid the development of the screening tool, and enable the early identification of Australian Army personnel who are at risk of having their personal relationship break down. Several of the known relationship stressors are relevant to other ‘high intensity’ professions, such as paramedics. Personal experience as an Army Officer has helped to highlight the importance of this research, and the benefits of developing a tool tailored to the unique social microclimate that is the Australian Army are clear. This research is, to the author’s knowledge, unique in the Australian context.

On the Security of Two RFID Mutual Authentication Protocols

In this paper, the security of two recent RFID mutual authentication protocols are investigated. The first protocol is a scheme proposed by Huang et al. [7] and the second one by Huang, Lin and Li [6]. We show that these two protocols have several weaknesses. In Huang et al.’s scheme, an adversary can determine the 32-bit secret password with a probability of 2−2 , and in Huang-Lin-Li scheme, a passive adversary can recognize a target tag with a success probability of 1−2−4 and an active adversary can determine all 32 bits of Access password with success probability of 2−4 . The computational complexity of these attacks is negligible.

On the Collision and Preimage Resistance of Certain Two-Call Hash Functions

In this paper we present concrete collision and preimage attacks on a large class of compression function constructions making two calls to the underlying ideal primitives. The complexity of the collision attack is above the theoretical lower bound for constructions of this type, but below the birthday complexity; the complexity of the preimage attack, however, is equal to the theoretical lower bound. We also present undesirable properties of some of Stam’s compression functions proposed at CRYPTO ’08. We show that when one of the n-bit to n-bit components of the proposed 2n-bit to n-bit compression function is replaced by a fixed-key cipher in the Davies-Meyer mode, the complexity of finding a preimage would be 2 n/3. We also show that the complexity of finding a collision in a variant of the 3n-bits to 2n-bits scheme with its output truncated to 3n/2 bits is 2 n/2. The complexity of our preimage attack on this hash function is about 2 n . Finally, we present a collision attack on a variant of the proposed m + s-bit to s-bit scheme, truncated to s − 1 bits, with a complexity of O(1). However, none of our results compromise Stam’s security claims.

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300 oC for 1 h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-Infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, C-O stretching of syringyl ring and aromatic C-H deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Reflection on the SIA Ltd professional project and the body of knowledge

In the last five years the Safety Institute of Australia Limited (SIA) has developed and implemented a number of strategies to gain professional recognition for the ‘generalist occupational health and safety (OHS) professional’ in Australia and internationally. Despite a considerable amount of work by the SIA aimed at gaining professional status, there does not appear to have been any published debate or reflection about how the drive for professionalism (the ‘professional project’) will contribute to the prevention of occupational disease and injury. Professionalisation has been promoted as a sign of maturity for the SIA and as an unquestionably good outcome, as it has been assumed that professionalisation will provide unmitigated benefits for workplace health and safety. The aim of this paper is to critically reflect on the processes of professionalisation (the professional project) and discuss the ways in which this project may shape the field of occupational health and safety.

The influence of internal load density on the energy and thermal performance of air-conditioned office buildings in the face of global warming

Internal heat sources may not only consume energy directly through their operation (e.g. lighting), but also contribute to building cooling or heating loads, which indirectly change building cooling and heating energy. Through the use of building simulation technique, this paper investigates the influence of building internal load densities on the energy and thermal performance of air conditioned office buildings in Australia. Case studies for air conditioned office buildings in major Australian capital cities are presented. It is found that with a decrease of internal load density in lighting and/or plug load, both the building cooling load and total energy use can be significantly reduced. Their effect on overheating hour reduction would be dependent on the local climate. In particular, it is found that if the building total internal load density is reduced from the base case of “medium” to “extra–low, the building total energy use under the future 2070 high scenario can be reduced by up to 89 to 120 kWh/m² per annum and the overheating problem could be completely avoided. It is suggested that the reduction in building internal load densities could be adopted as one of adaptation strategies for buildings in face of the future global warming.

Foreign-currency and monetary geopolitics of United States and its effects on the future of the international system

The US dollar is still considered as the main strategic deposit among the currencies of different countries of the world and the policies of the World Bank and the International Financial Organizations have been and will always be influenced by the US economy. Despite the economic crises and commercial balance deficits in the United States, dollar has maintained its high position in and its domination over foreign exchanges and foreign-currency deposits of the countries. The novelty of the present research relies on its consideration of the political properties of the governments and the geopolitical effects of these countries on the position of their monetary and foreign-currency policies and consequently, on the international financial organizations such as the International Monetary Fund and the World Bank, which can determine the future of international economy and the political relations among countries. Our research proves that the political development of the United States and its geopolitical situation have been of the effective factors on dollar growth; and unless the competitors acquire such a relative advantage, they will not be able to seriously challenge the currency of dollar and the monetary policies of the United States, at least in a short time

Geo-economics and considerations on the tourism industry with emphasis on historical cities tourism and ecotourism in Iran

Considering its many potentials in the tourism industry, Iran has constantly been among the leading countries seeking development in this industry. Iran is a country with many attractions in different tourism sections including cultural, urban, and monument tourism, and ancient places as well as ecotourism, and water tourism etc. for tourists. However, Iran has never economically prospered regarding its potentials in this industry as compared to its rivals. Thus, the main objective of this work is to list the main necessities of harnessing economic power and required instruments to fulfill this goal. In addition, the tourism industry is discussed as an important strategy for reaching this power, and the Iranian wildlife is introduced as an intact environment. It is also discussed that what economic benefits are obtained through using this tourism industry. It must be noted that the main emphasis of this work is on urban, monument tourism, ancient places, and ecotourism as a case study in two Iranian provinces. Finally, the required analyses are performed considering the affinity between these two sections and two provinces. Results indicated that while Iran having the highest percent of growth compared to the two other countries active in this area, however this advantage has not significantly affected the GDP in Iran, and Iran has not been able to improve its geo-economic capacity in this area.

Changing influences on the concept of ‘media influence’

The concept of media influence has a long history in media and communication studies, and has also had significant influence on public policy. This article revisits questions of media influence through three short case studies. First, it critically analyses the strongly partisan position of News Corporation’s newspapers against the Labor government during the 2013 Australian Federal election to consider whether the potential for media influence equated to the effective use of media power. Second, it discusses the assumption in broadcasting legislation, in both the United Kingdom and Australia, that terrestrial broadcasting should be subject to more content regulation than subscription services, and notes the new challenges arising from digital television and over-the-top video streaming services. Finally, it discusses the rise of multi-platform global content aggregators such as Google, Apple, Microsoft and others, and how their rise necessitates changes in ways of thinking about concentration of media ownership, and regulations that may ensue from it.

Perspectives on Australian bankruptcy law through the prism of the World Bank report on the treatment of the insolvency of natural persons

The insolvency of natural persons raises questions not only for a nation’s economy but also for its concern for equity. The World Bank has recently released a Report on the Treatment of the Insolvency of Natural Persons to guide nations in addressing the issues raised by an individual debtor’s insolvency. A brief review of Australia’s personal insolvency laws shows that it addresses many of the issues raised by the Report. However two areas are identified as worthy of further investigation by policy-makers and scholars to better address a concern for equity.

On the use of optical flow for scene change detection and description

We propose the use of optical flow information as a method for detecting and describing changes in the environment, from the perspective of a mobile camera. We analyze the characteristics of the optical flow signal and demonstrate how robust flow vectors can be generated and used for the detection of depth discontinuities and appearance changes at key locations. To successfully achieve this task, a full discussion on camera positioning, distortion compensation, noise filtering, and parameter estimation is presented. We then extract statistical attributes from the flow signal to describe the location of the scene changes. We also employ clustering and dominant shape of vectors to increase the descriptiveness. Once a database of nodes (where a node is a detected scene change) and their corresponding flow features is created, matching can be performed whenever nodes are encountered, such that topological localization can be achieved. We retrieve the most likely node according to the Mahalanobis and Chi-square distances between the current frame and the database. The results illustrate the applicability of the technique for detecting and describing scene changes in diverse lighting conditions, considering indoor and outdoor environments and different robot platforms.