Raman spectroscopic characteristics of phthalocyanine and naphthalocyanine in sandwich-type phthalocyaninato and porphyrinato rare earth complexes Part 5. – Raman spectroscopic characteristics of naphthalocyanine in mixed [tetrakis(4-tert-butylphenyl)porphyrinato]-(naphthalocyaninato) rare earth double-deckers

Raman spectra were recorded in the range 400–1800 cm−1 for a series of 15 mixed \[tetrakis(4-tert-butylphenyl)porphyrinato](2,3-naphthalocyaninato) rare earth double-deckers M(TBPP)(Nc) (M = Y; La–Lu except Pm) using laser excitation at 632.8 and 785 nm. Comparisons with bis(naphthalocyaninato) rare earth counterparts reveal that the vibrations of the metallonaphthalocyanine M(Nc) fragment dominate the Raman features of M(TBPP)(Nc). When excited with radiation of 632.8 nm, the most intense vibration appears at about 1595 cm−1, due to the naphthalene stretching. These complexes exhibit the marker Raman band for Nc•− as a medium-intense band in the range 1496–1507 cm−1, attributed to the coupling of pyrrole and aza stretching, while the marker Raman band of Nc2− in intermediate-valence Ce(TBPP)(Nc) appears as a strong band at 1493 cm−1 and is due to the isoindole stretchings. By contrast, when excited with radiation of 785 nm that is in close resonance with the main Q absorption band of the naphthalocyanine ligand, the ring radial vibrations at ca 680 and 735 cm−1 for MIII(TBPP)(Nc) are selectively intensified and are the most intense bands. For the cerium double-decker, the most intense vibration also acting as the marker Raman band of Nc2− appears at 1497 cm−1 with contributions from both pyrrole CC and aza CN stretches. The same vibrational modes show weak to medium intensity scattering at 1506–1509 cm−1 for MIII(TBPP)(Nc) and this is the marker Raman band of Nc•− when thus excited. The scatterings due to the Nc breathings, ring radial vibration, aza group stretchings, naphthalene stretchings, benzoisoindole stretchings and the coupling of pyrrole CC and aza CN stretchings in MIII(TBPP)(Nc) are all slightly blue shifted along with the decrease in rare earth ionic radius, confirming the effects of increased ring–ring interactions on the Raman characteristics of naphthalocyanine in the mixed ring double-deckers.

Planning and implementing trajectories for autonomous underwater vehicles to track evolving ocean processes based on predictions from a regional ocean model

Path planning and trajectory design for autonomous underwater vehicles (AUVs) is of great importance to the oceanographic research community because automated data collection is becoming more prevalent. Intelligent planning is required to maneuver a vehicle to high-valued locations to perform data collection. In this paper, we present algorithms that determine paths for AUVs to track evolving features of interest in the ocean by considering the output of predictive ocean models. While traversing the computed path, the vehicle provides near-real-time, in situ measurements back to the model, with the intent to increase the skill of future predictions in the local region. The results presented here extend prelim- inary developments of the path planning portion of an end-to-end autonomous prediction and tasking system for aquatic, mobile sensor networks. This extension is the incorporation of multiple vehicles to track the centroid and the boundary of the extent of a feature of interest. Similar algorithms to those presented here are under development to consider additional locations for multiple types of features. The primary focus here is on algorithm development utilizing model predictions to assist in solving the motion planning problem of steering an AUV to high-valued locations, with respect to the data desired. We discuss the design technique to generate the paths, present simulation results and provide experimental data from field deployments for tracking dynamic features by use of an AUV in the Southern California coastal ocean.

Local Rademacher complexities

We propose new bounds on the error of learning algorithms in terms of a data-dependent notion of complexity. The estimates we establish give optimal rates and are based on a local and empirical version of Rademacher averages, in the sense that the Rademacher averages are computed from the data, on a subset of functions with small empirical error. We present some applications to classification and prediction with convex function classes, and with kernel classes in particular.

Crushing

In this video, phrases float around the screen offering a heartfelt account of a failed romance. Accompanied by a stock music piano soundtrack, the words initially flow at a readable pace. However, as the video progresses, the screen becomes more intensely filled with text so that it cannot be read all at once. This work engages with the signifying processes of romantic clichés. It questions how we communicate grand ideas and emotions using words that seem to have all their sincerity sucked dry. By emphasizing the constructed nature of communication, and by problematizing the process of reading, this work draws attention to the fragmentary and dissociated processes that pervade signifying acts.

Thermal stability of stercorite H(NH4)Na(PO4)·4H2O – a cave mineral from Petrogale Cave, Madura, Eucla, Western Australia

Thermogravimetric analysis has been used to determine the thermal stability of the mineral stercorite H(NH4)Na(PO4)·4H2O. The mineral stercorite originated from the Petrogale Cave, Madura, Eucla, Western Australia. This cave is one of many caves in the Nullarbor Plain in the South of Western Australia. The mineral is formed by the reaction of bat guano chemicals on calcite substrates. Upon thermal treatment the mineral shows a strong decomposition at 191°C with loss of water and ammonia. Other mass loss steps are observed at 158, 317 and 477°C. Ion current curves indicate a gain of CO2 at higher temperature and are attributed to the thermal decomposition of calcite impurity.

Physically sound vehicle-driver model for realistic microscopic simulation

In microscopic traffic simulators, the interaction between vehicles is considered. The dynamics of the system then becomes an emergent property of the interaction between its components. Such interactions include lane-changing, car-following behaviours and intersection management. Although, in some cases, such simulators produce realistic prediction, they do not allow for an important aspect of the dynamics, that is, the driver-vehicle interaction. This paper introduces a physically sound vehicle-driver model for realistic microscopic simulation. By building a nanoscopic traffic simulation model that uses steering angle and throttle position as parameters, the model aims to overcome unrealistic acceleration and deceleration values, as found in various microscopic simulation tools. A physics engine calculates the driving force of the vehicle, and the preliminary results presented here, show that, through a realistic driver-vehicle-environment simulator, it becomes possible to model realistic driver and vehicle behaviours in a traffic simulation.

Advances and future directions for management of trauma patients with musculoskeletal injuries

Musculoskeletal injuries are the most common reason for operative procedures in severely injured patients and are major determinants of functional outcomes. In this paper, we summarise advances and future directions for management of multiply injured patients with major musculoskeletal trauma. Improved understanding of fracture healing has created new possibilities for management of particularly challenging problems, such as delayed union and non union of fractures and large bone defects. Optimum timing of major orthopaedic interventions is guided by increased knowledge about the immune response after injury. Individual treatment should be guided by trading off the benefits of early definitive skeletal stabilisation, and the potentially life-threatening risks of systemic complications such as fat embolism, acute lung injury, and multiple organ failure. New methods for measurement of fracture healing and function and quality of life outcomes pave the way for landmark trials that will guide the future management of musculoskeletal injuries.

Data transformations in custom digital workflows : property graphs as a data model for user-defined mappings

This paper describes the use of property graphs for mapping data between AEC software tools, which are not linked by common data formats and/or other interoperability measures. The intention of introducing this in practice, education and research is to facilitate the use of diverse, non-integrated design and analysis applications by a variety of users who need to create customised digital workflows, including those who are not expert programmers. Data model types are examined by way of supporting the choice of directed, attributed, multi-relational graphs for such data transformation tasks. A brief exemplar design scenario is also presented to illustrate the concepts and methods proposed, and conclusions are drawn regarding the feasibility of this approach and directions for further research.

Assessment of the molecular structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O using vibrational spectroscopy

The structure of the borate mineral sakhaite Ca12Mg4(BO3)7(CO3)4Cl(OH)2·H2O, a borate–carbonate of calcium and magnesium has been assessed using vibrational spectroscopy. Assignment of bands is undertaken by comparison with the data from other published results. Intense Raman band at 1134 cm−1 with a shoulder at 1123 cm−1 is assigned to the symmetric stretching mode. The Raman spectrum displays bands at 1479, 1524 and 1560 cm−1 which are assigned to the antisymmetric stretching vibrations. The observation of multiple carbonate stretching bands supports the concept that the carbonate units are non-equivalent. The Raman band at 968 cm−1 with a shoulder at 950 cm−1 is assigned to the symmetric stretching mode of trigonal boron. Raman bands at 627 and 651 cm−1 are assigned to the out-of-plane bending modes of trigonal and tetrahedral boron. Raman spectroscopy coupled with infrared spectroscopy enables the molecular structure of the mineral sakhaite to be assessed.

An analysis of the KEEP CLEAR pavement markings effects on queuing vehicles dynamic performance at urban signalised intersections

KEEP CLEAR pavement markings are widely used at urban signalised intersections to indicate to drivers to avoid entering blocked intersections. For example, ‘Box junctions’ are most widely used in the United Kingdom and other European countries. However, in Australia, KEEP CLEAR markings are mostly used to improve access from side roads onto a main road, especially when the side road is very close to a signalised intersection. This paper aims to reveal how the KEEP CLEAR markings affect the dynamic performance of the queuing vehicles on the main road, where the side road access is near a signalised intersection. Raw traffic field data was collected from an intersection at the Gold Coast, Australia, and the Kanade–Lucas–Tomasi (KLT) feature tracker approach was used to extract dynamic vehicle data from the raw video footage. The data analysis reveals that the KEEP CLEAR markings generate positive effects on the queuing vehicles in discharge on the main road. This finding refutes the traditional viewpoint that the KEEP CLEAR pavement markings will cause delay for the queuing vehicles’ departure due to the enlarged queue spacing. Further studies are suggested in this paper as well.

Exploring subscription renewal intention of operational cloud enterprise systems - a stakeholder perspective

Retaining customers is a relevant topic throughout all service industries. However, only limited attention has been directed towards studying the antecedents of subscription renewal in the context of operational cloud enterprise systems. Cloud services have historically been offered as subscription-based services with the (theoretical) possibility of seamless service cancellation, in contrast to classical IT-Outsourcing contracts or license-based software installations of on-premise enterprise systems. In this work, we investigate the central concept of subscription renewal by focusing on different facets of IS success and their relevance for distinct employee cohorts. Analyzing inter-cohort differences has strong practical implications, as it helps IT vendors to focus on specific IT-related factors when trying to retain customers. Therefore an empirical study was undertaken. The hypotheses were developed on an individual level and tested using survey responses of IT decision makers within companies which adopted cloud enterprise systems. Gathered data was then analyzed using PLS. The results show that subscription renewal intention of the strategic cohort is mainly based on perceived system quality, whereas information quality explains most of the variance of subscription renewal in the management cohort. Beneath the cloud enterprise systems specific contributions, the work adds to the theoretical body of research related to IS success and IS continuation, as well as stakeholder perspectives.

Effect of pretreatment on saccharification of sugarcane bagasse by complex and simple enzyme mixtures

Saccharification of sugarcane bagasse pretreated at the pilot-scale with different processes (in combination with steam-explosion) was evaluated. Maximum glucan conversion with Celluclast 1.5 L (15–25 FPU/g glucan) was in the following order: glycerol/HCl > HCl > H2SO4 > NaOH, with the glycerol system achieving ∼100% conversion. Surprisingly, the NaOH substrate achieved optimum saccharification with only 8 FPU/g glucan. Glucan conversions (3.6–6%) obtained with mixtures of endo-1,4-β-glucanase (EG) and β-glucosidase (βG) for the NaOH substrate were 2–6 times that of acid substrates. However, glucan conversions (15–60%) obtained with mixtures of cellobiohydrolase (CBH I) and βG on acidified glycerol substrate were 10–30% higher than those obtained for NaOH and acid substrates. The susceptibility of the substrates to enzymatic saccharification was explained by their physical and chemical attributes. Acidified glycerol pretreatment offers the opportunity to simplify the complexity of enzyme mixtures required for saccharification of lignocellulosics.