Time-Dependent Density Functional Molecular Orbital and Excited State Calculations on Bis(porphyrinyl)butadiynes in the Monocationic, Neutral, Monoanionic, and Dianionic Oxidation States

We report a theoretical study of the multiple oxidation states (1+, 0, 1−, and 2−) of a meso,meso-linked diporphyrin, namely bis[10,15,20-triphenylporphyrinatozinc(II)-5-yl]butadiyne (4), using Time-Dependent Density Functional Theory (TDDFT). The origin of electronic transitions of singlet excited states is discussed in comparison to experimental spectra for the corresponding oxidation states of the close analogue bis{10,15,20-tris[3‘,5‘-di-tert-butylphenyl]porphyrinatozinc(II)-5-yl}butadiyne (3). The latter were measured in previous work under in situ spectroelectrochemical conditions. Excitation energies and orbital compositions of the excited states were obtained for these large delocalized aromatic radicals, which are unique examples of organic mixed-valence systems. The radical cations and anions of butadiyne-bridged diporphyrins such as 3 display characteristic electronic absorption bands in the near-IR region, which have been successfully predicted with use of these computational methods. The radicals are clearly of the “fully delocalized” or Class III type. The key spectral features of the neutral and dianionic states were also reproduced, although due to the large size of these molecules, quantitative agreement of energies with observations is not as good in the blue end of the visible region. The TDDFT calculations are largely in accord with a previous empirical model for the spectra, which was based simplistically on one-electron transitions among the eight key frontier orbitals of the C4 (1,4-butadiyne) linked diporphyrins.

Implicit difference approximation for the time fractional diffusion equation

In this paper, we consider a time fractional diffusion equation on a finite domain. The equation is obtained from the standard diffusion equation by replacing the first-order time derivative by a fractional derivative (of order $0<\alpha<1$ ). We propose a computationally effective implicit difference approximation to solve the time fractional diffusion equation. Stability and convergence of the method are discussed. We prove that the implicit difference approximation (IDA) is unconditionally stable, and the IDA is convergent with $O(\tau+h^2)$, where $\tau$ and $h$ are time and space steps, respectively. Some numerical examples are presented to show the application of the present technique.

Doing Time in the Retail Industry

This paper uses survey data to explore employee satisfaction with working time arrangements within a large supermarket chain in Queensland. The findings confirm those in the literature that employees have a diverse range of working time preferences, and that employees will be more satisfied if those preferences are met by their employer. In general, many full-time employees wanted shorter hours and a sizeable proportion of part-time employees wanted longer working hours. This paper is a preliminary attempt at teasing out the explanations behind working time preferences.

Radiographic outcomes over time after endoscopic anterior scoliosis correction

A prospective, consecutive series of 106 patients receiving endoscopic anterior scoliosis correction. The aim was to analyse changes in radiographic parameters and rib hump in the two years following surgery. Endoscopic anterior scoliosis correction is a level sparing approach, therefore it is important to assess the amount of decompensation which occurs after surgery. All patients received a single anterior rod and vertebral body screws using a standard compression technique. Cleared disc spaces were packed with either mulched femoral head allograft or rib head/iliac crest autograft. Radiographic parameters (major, instrumented, minor Cobb, T5-T12 kyphosis) and rib hump were measured at 2,6,12 and 24 months after surgery. Paired t-tests and Wilcoxon signed ranks tests were used to assess the statistical significant of changes between adjacent time intervals.----- Results: Mean loss of major curve correction from 2 to 24 months after surgery was 4 degrees. Mean loss of rib hump correction was 1.4 degrees. Mean sagittal kyphosis increased from 27 degrees at 2 months to 30.6 degrees at 24 months. Rod fractures and screw-related complications resulted in several degrees less correction than patients without complications, but overall there was no clinically significant decompensation following complications. The study concluded that there are small changes in deformity measures after endoscopic anterior scoliosis surgery, which are statistically significant but not clinically significant.

Creating a therapeutic environment : a non-randomised controlled trial of a quiet time intervention for patients in acute care

Background: Noise is a significant barrier to sleep for acute care hospital patients, and sleep has been shown to be therapeutic for health, healing and recovery. Scheduled quiet time interventions to promote inpatient rest and sleep have been successfully trialled in critical care but not in acute care settings. Objectives: The study aim was to evaluate as cheduled quiet time intervention in an acute care setting. The study measured the effect of a scheduled quiet time on noise levels, inpatients’ rest and sleep behaviour, and wellbeing. The study also examined the impact of the intervention on patients’, visitors’ and health professionals’ satisfaction, and organisational functioning. Design: The study was a multi-centred non-randomised parallel group trial. Settings: The research was conducted in the acute orthopaedic wards of two major urban public hospitals in Brisbane, Australia. Participants: All patientsadmitted to the two wards in the5-month period of the study were invited to participate, withafinalsample of 299 participants recruited. This sample produced an effect size of 0.89 for an increase in the number of patients asleep during the quiet time. Methods: Demographic data were collected to enable comparison between groups. Data for noise level, sleep status, sleepiness and well being were collected using previously validated instruments: a Castle Model 824 digital sound level indicator; a three point sleep status scale; the Epworth Sleepiness Scale; and the SF12 V2 questionnaire. The staff, patient and visitor surveys on the experimental ward were adapted from published instruments. Results: Significant differences were found between the two groups in mean decibel level and numbers of patients awake and asleep. The difference in mean measured noise levels between the two environments corresponded to a ‘perceived’ difference of 2 to 1. There were significant correlations between average decibel level and number of patients awake and asleep in the experimental group, and between average decibel level and number of patients awake in the control group. Overall, patients, visitors and health professionals were satisfied with the quiet time intervention. Conclusions: The findings show that a quiet time intervention on an acute care hospital ward can affect noise level and patient sleep/wake patterns during the intervention period. The overall strongly positive response from surveys suggests that scheduled quiet time would be a positively perceived intervention with therapeutic benefit.

Delay-dependent robust H-infinity control for uncertain systems with time-varying delay

This paper proposes a new approach for delay-dependent robust H-infinity stability analysis and control synthesis of uncertain systems with time-varying delay. The key features of the approach include the introduction of a new Lyapunov–Krasovskii functional, the construction of an augmented matrix with uncorrelated terms, and the employment of a tighter bounding technique. As a result, significant performance improvement is achieved in system analysis and synthesis without using either free weighting matrices or model transformation. Examples are given to demonstrate the effectiveness of the proposed approach.

School students and part-time work: Workplace problems and challenges.

This paper uses data from a large national project on student-working to examine problems and challenges for school students working in part-time jobs. While literature has identified some potential problems and challenges, and some potential difficulties can be extrapolated from the nature of a young teenage workforce and the nature of the workplaces, these were largely absent in the two companies researched because the companies already had policies in place that addressed the potential problems. Some suggestions are made about how problems and challenges could be avoided in a wider range of adolescent workplaces.

An inverse time admittance relay for fault detection in distribution networks containing DGs

Isolation of a faulted segment, from either side of a fault, in a radial feeder that has several converter interfaced DGs is a challenging task when current sensing protective devices are employed. The protective device, even if it senses a downstream fault, may not operate if fault current level is low due to the current limiting operation of converters. In this paper, a new inverse type relay is introduced based on line admittance measurement to protect a distribution network, which has several converter interfaced DGs. The basic operation of this relay, its grading and reach settings are explained. Moreover a method is proposed to compensate the fault resistance such that the relay operation under this condition is reliable. Then designed relay performances are evaluated in a radial distribution network. The results are validated through PSCAD/EMTDC simulation and MATLAB calculations.

The effect of insertion time on the axial pullout strength of anterior vertebral body screws

Top screw pullout occurs when the screw is under too much axial force to remain secure in the vertebral body. In vitro biomechanical pullout tests are commonly done to find the maximum fixation strength of anterior vertebral body screws. Typically, pullout tests are done instantaneously where the screw is inserted and then pulled out immediately after insertion. However, bone is a viscoelastic material so it shows a time dependent stress and strain response. Because of this property, it was hypothesised that creep occurs in the vertebral trabecular bone due to the stress caused by the screw. The objective of this study was therefore to determine whether the axial pullout strength of anterior vertebral body screws used for scoliosis correction surgery changes with time after insertion. This study found that there is a possible relationship between pullout strength and time; however more testing is required as the sample numbers were quite small. The design of the screw is made with the knowledge of the strength it must obtain. This is important to prevent such occurrences as top screw pullout. If the pullout strength is indeed decreased due to creep, the design of the screw may need to be changed to withstand greater forces.

A time-variant medical data trustworthiness assessment model

Electronic Health Record (EHR) systems are being introduced to overcome the limitations associated with paper-based and isolated Electronic Medical Record (EMR) systems. This is accomplished by aggregating medical data and consolidating them in one digital repository. Though an EHR system provides obvious functional benefits, there is a growing concern about the privacy and reliability (trustworthiness) of Electronic Health Records. Security requirements such as confidentiality, integrity, and availability can be satisfied by traditional hard security mechanisms. However, measuring data trustworthiness from the perspective of data entry is an issue that cannot be solved with traditional mechanisms, especially since degrees of trust change over time. In this paper, we introduce a Time-variant Medical Data Trustworthiness (TMDT) assessment model to evaluate the trustworthiness of medical data by evaluating the trustworthiness of its sources, namely the healthcare organisation where the data was created and the medical practitioner who diagnosed the patient and authorised entry of this data into the patient’s medical record, with respect to a certain period of time. The result can then be used by the EHR system to manipulate health record metadata to alert medical practitioners relying on the information to possible reliability problems.

Application of system dynamics for evaluating truck load regulations in Anhui, China

In the critical situation of prevailing overweight transportation and crag-fast enforcement in Chinese highway networks, this paper develops a methodological framework for truck weight regulation (TWR) evaluation using System Dynamics (SD). Composed of five interrelated subsystems, the framework is able to capture the highway, vehicle and freight variables that influence the effect of TWR and transportation efficiency over time. It specifically describes the development and use of the Truck Weight Regulation Evaluating Model (TWREM) for the highway freight system in Anhui province, China. Three policy alternatives are analyzed: 1) tolerant policy approach, which allows heavy-duty freight activity to continue in its current state, and is shown to lead to nearly catastrophic results; 2) rigid policy approach, which would terminate all heavy-duty freight activities immediately, and is shown to be economically infeasible; and 3) moderate policy approach, which advocates a gradual reduction of heavy-duty freight activities to a moderate state. The simulation results shows that the moderate policy approach is the most appropriate option to solve the social and economic problems arising from the activities of the heavy-duty freight transportation in Anhui. In addition, some suggestions of TWR policy in China are also made in this paper.