Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

Tuning the surface structure of nitrogen-doped TiO2Nanofibres : an effective method to rnhance photocatalytic activities of visible-light-driven green synthesis and degradation

Nitrogen-doped TiO2 nanofibres of anatase and TiO2(B) phases were synthesised by a reaction between titanate nanofibres of a layered structure and gaseous NH3 at 400–700 °C, following a different mechanism than that for the direct nitrogen doping from TiO2. The surface of the N-doped TiO2 nanofibres can be tuned by facial calcination in air to remove the surface-bonded N species, whereas the core remains N doped. N-Doped TiO2 nanofibres, only after calcination in air, became effective photocatalysts for the decomposition of sulforhodamine B under visible-light irradiation. The surface-oxidised surface layer was proven to be very effective for organic molecule adsorption, and the activation of oxygen molecules, whereas the remaining N-doped interior of the fibres strongly absorbed visible light, resulting in the generation of electrons and holes. The N-doped nanofibres were also used as supports of gold nanoparticle (Au NP) photocatalysts for visible-light-driven hydroamination of phenylacetylene with aniline. Phenylacetylene was activated on the N-doped surface of the nanofibres and aniline on the Au NPs. The Au NPs adsorbed on N-doped TiO2(B) nanofibres exhibited much better conversion (80 % of phenylacetylene) than when adsorbed on undoped fibres (46 %) at 40 °C and 95 % of the product is the desired imine. The surface N species can prevent the adsorption of O2 that is unfavourable for the hydroamination reaction, and thus, improve the photocatalytic activity. Removal of the surface N species resulted in a sharp decrease of the photocatalytic activity. These photocatalysts are feasible for practical applications, because they can be easily dispersed into solution and separated from a liquid by filtration, sedimentation or centrifugation due to their fibril morphology.

The role of common but differentiated responsibility in the 2020 climate regime

The principle of common but differentiated responsibility (CBDR) will play a role in the 2020 Climate Regime. This Article starts by examining differential treatment within the international legal order, finding that it is ethically and practically difficult to implement an international climate instrument based on formal equality. There is evidence of state parties accepting differential responsibilities in a number of areas within the international legal order and the embedding of CBDR in the United Nations Framework Convention on Climate Change (UNFCCC), means that that differential commitments will lie at the heart of the 2020 climate regime. The UNFCCC applies the implementation method of differentiation, while the Kyoto Protocol applies both the obligation and implementation method of differentiation. It is suggested that the implementation model will be the differentiation model retained in the 2020 climate agreement. The Parties’ submissions under the Durban Platform are considered in order to gain an understanding of their positions on CBDR. While there are areas of contention including the role of principles in shaping obligations and the ongoing legal status of Annex I and Non-Annex I distinction, there is broad consensus among the parties in favour of differentiation by implementation with developed and major economies undertaking Quantified Emission Limitation and Reduction Objectives (economy wide targets) and developing countries that are not major economies undertaking sectoral targets.

High-growth firms : characteristics, job contribution and method observations

Largely as a result of mass unemployment problems in many European countries, the dynamics of job creation has in recent years attracted increased interest on the part of academics as well as policy-makers. In connection to this, a large number of studies carried out in various countries have concluded that SMEs play a very large and/or growing role as job creators (Birch, 1979; Baldwin and Picot, 1995; Davidsson, 1995a; Davidsson, Lindmark and Olofsson, 1993; 1994; 1995; 1997a; 1997b; Fumagelli and Mussati, 1993; Kirchhoff and Phillips, 1988; Spilling, 1995; for further reference to studies carried out in a large number of countries see also Aiginger and Tichy, 1991; ENSR, 1994; Loveman and Sengenberger, 1991; OECD, 1987; Storey and Johnson, 1987). While most researchers agree on the importance of SMEs, there is some controversy as regards whether this is mainly a result of many small start-ups and incremental expansions, or if a small minority of high growth SMEs contribute the lion’s share of new employment. This is known as the ‘mice vs. gazelles’ or ‘flyers vs. trundlers’ debate. Storey strongly advocates the position that the small group of high growth SMEs are the ‘real’ job creators (Storey, 1994; Storey & Johnson, 1987), whereas, e.g., the Davidsson et al research in Sweden (cf. above) gives more support for the ‘mice’ hypothesis.

A finite volume method with linearisation in time for the solution of advection-reaction-diffusion systems

The numerical solution in one space dimension of advection--reaction--diffusion systems with nonlinear source terms may invoke a high computational cost when the presently available methods are used. Numerous examples of finite volume schemes with high order spatial discretisations together with various techniques for the approximation of the advection term can be found in the literature. Almost all such techniques result in a nonlinear system of equations as a consequence of the finite volume discretisation especially when there are nonlinear source terms in the associated partial differential equation models. This work introduces a new technique that avoids having such nonlinear systems of equations generated by the spatial discretisation process when nonlinear source terms in the model equations can be expanded in positive powers of the dependent function of interest. The basis of this method is a new linearisation technique for the temporal integration of the nonlinear source terms as a supplementation of a more typical finite volume method. The resulting linear system of equations is shown to be both accurate and significantly faster than methods that necessitate the use of solvers for nonlinear system of equations.

A deconvolution method for deriving the transit time spectrum for ultrasound propagation through cancellous bone replica models

The acceptance of broadband ultrasound attenuation for the assessment of osteoporosis suffers from a limited understanding of ultrasound wave propagation through cancellous bone. It has recently been proposed that the ultrasound wave propagation can be described by a concept of parallel sonic rays. This concept approximates the detected transmission signal to be the superposition of all sonic rays that travel directly from transmitting to receiving transducer. The transit time of each ray is defined by the proportion of bone and marrow propagated. An ultrasound transit time spectrum describes the proportion of sonic rays having a particular transit time, effectively describing lateral inhomogeneity of transit times over the surface of the receiving ultrasound transducer. The aim of this study was to provide a proof of concept that a transit time spectrum may be derived from digital deconvolution of input and output ultrasound signals. We have applied the active-set method deconvolution algorithm to determine the ultrasound transit time spectra in the three orthogonal directions of four cancellous bone replica samples and have compared experimental data with the prediction from the computer simulation. The agreement between experimental and predicted ultrasound transit time spectrum analyses derived from Bland–Altman analysis ranged from 92% to 99%, thereby supporting the concept of parallel sonic rays for ultrasound propagation in cancellous bone. In addition to further validation of the parallel sonic ray concept, this technique offers the opportunity to consider quantitative characterisation of the material and structural properties of cancellous bone, not previously available utilising ultrasound.

Working together-apart : exploring the relationships between formal and informal care networks for people dying at home

Introduction Informal caring networks contribute significantly to end-of-life (EOL) care in the community. However, to ensure that these networks are sustainable, and unpaid carers are not exploited, primary carers need permission and practical assistance to gather networks together and negotiate the help they need. Our aim in this study was to develop an understanding of how formal and informal carers work together when care is being provided in a dying person's home. We were particularly interested in formal providers’ perceptions and knowledge of informal networks of care and in identifying barriers to the networks working together. Methods Qualitative methods, informed by an interpretive approach, were used. In February-July 2012, 10 focus groups were conducted in urban, regional, and rural Australia comprising 88 participants. Findings Our findings show that formal providers are aware, and supportive, of the vital role informal networks play in the care of the dying at home. A number of barriers to formal and informal networks working together more effectively were identified. In particular, we found that the Australian policy of health-promoting palliative is not substantially translating to practice. Conclusion Combinations of formal and informal caring networks are essential to support people and their primary carers. Formal service providers do little to establish, support, or maintain the informal networks although there is much goodwill and scope for them to do so. Further re-orientation towards a health-promoting palliative care and community capacity building approach is suggested.

A finite volume method for solving the two-sided time-space fractional advection-dispersion equation

We present a finite volume method to solve the time-space two-sided fractional advection-dispersion equation on a one-dimensional domain. The spatial discretisation employs fractionally-shifted Grünwald formulas to discretise the Riemann-Liouville fractional derivatives at control volume faces in terms of function values at the nodes. We demonstrate how the finite volume formulation provides a natural, convenient and accurate means of discretising this equation in conservative form, compared to using a conventional finite difference approach. Results of numerical experiments are presented to demonstrate the effectiveness of the approach.

A rule-based hybrid method for anomaly detection in online-social-network graphs

Detecting anomalies in the online social network is a significant task as it assists in revealing the useful and interesting information about the user behavior on the network. This paper proposes a rule-based hybrid method using graph theory, Fuzzy clustering and Fuzzy rules for modeling user relationships inherent in online-social-network and for identifying anomalies. Fuzzy C-Means clustering is used to cluster the data and Fuzzy inference engine is used to generate rules based on the cluster behavior. The proposed method is able to achieve improved accuracy for identifying anomalies in comparison to existing methods.

Novel sequential methods in dose-finding designs : extensions of the continual reassessment method

Dose-finding trials are a form of clinical data collection process in which the primary objective is to estimate an optimum dose of an investigational new drug when given to a patient. This thesis develops and explores three novel dose-finding design methodologies. All design methodologies presented in this thesis are pragmatic. They use statistical models, incorporate clinicians' prior knowledge efficiently, and prematurely stop a trial for safety or futility reasons. Designing actual dose-finding trials using these methodologies will minimize practical difficulties, improve efficiency of dose estimation, be flexible to stop early and reduce possible patient discomfort or harm.

Tethering for Selective Synthesis of 2,2′-Biphenols : the Acetal Method

2,2'-Biphenols are a large and diverse group of compounds with exceptional properties both as ligands and bioactive agents. Traditional methods for their synthesis by oxidative dimerisation are often problematic and lead to mixtures of ortho- and para-connected regioisomers. To compound these issues, an intermolecular dimerisation strategy is often inappropriate for the synthesis of heterodimers. The ‘acetal method’ provides a solution for these problems: stepwise tethering of two monomeric phenols enables heterodimer synthesis, enforces ortho regioselectivity and allows relatively facile and selective intramolecular reactions to take place. The resulting dibenzo[1,3]dioxepines have been analysed by quantum chemical calculations to obtain information about the activation barrier for ring flip between the enantiomers. Hydrolytic removal of the dioxepine acetal unit revealed the 2,2′-biphenol target.

Police officer in-vehicle discomfort : appointments carriage method and vehicle seat features

Musculoskeletal pain is commonly reported by police officers. A potential cause of officer discomfort is a mismatch between vehicle seats and the method used for carrying appointments. Twenty-five police officers rated their discomfort while seated in: (1) a standard police vehicle seat, and (2) a vehicle seat custom-designed for police use. Discomfort was recorded in both seats while wearing police appointments on: (1) a traditional appointments belt, and (2) a load-bearing vest / belt combination (LBV). Sitting in the standard vehicle seat and carrying appointments on a traditional appointments belt were both associated with significantly elevated discomfort. Four vehicle seat features were most implicated as contributing to discomfort: back rest bolster prominence; lumbar region support; seat cushion width; and seat cushion bolster depth. Authorising the carriage of appointments using a LBV is a lower cost solution with potential to reduce officer discomfort. Furthermore, the introduction of custom-designed vehicle seats should be considered.

Spatially-explicit modelling of grassland classes - an improved method of integrating a climate-based classification model with interpolated climate surfaces

Spatially-explicit modelling of grassland classes is important to site-specific planning for improving grassland and environmental management over large areas. In this study, a climate-based grassland classification model, the Comprehensive and Sequential Classification System (CSCS) was integrated with spatially interpolated climate data to classify grassland in Gansu province, China. The study area is characterized by complex topographic features imposed by plateaus, high mountains, basins and deserts. To improve the quality of the interpolated climate data and the quality of the spatial classification over this complex topography, three linear regression methods, namely an analytic method based on multiple regression and residues (AMMRR), a modification of the AMMRR method through adding the effect of slope and aspect to the interpolation analysis (M-AMMRR) and a method which replaces the IDW approach for residue interpolation in M-AMMRR with an ordinary kriging approach (I-AMMRR), for interpolating climate variables were evaluated. The interpolation outcomes from the best interpolation method were then used in the CSCS model to classify the grassland in the study area. Climate variables interpolated included the annual cumulative temperature and annual total precipitation. The results indicated that the AMMRR and M-AMMRR methods generated acceptable climate surfaces but the best model fit and cross validation result were achieved by the I-AMMRR method. Twenty-six grassland classes were classified for the study area. The four grassland vegetation classes that covered more than half of the total study area were "cool temperate-arid temperate zonal semi-desert", "cool temperate-humid forest steppe and deciduous broad-leaved forest", "temperate-extra-arid temperate zonal desert", and "frigid per-humid rain tundra and alpine meadow". The vegetation classification map generated in this study provides spatial information on the locations and extents of the different grassland classes. This information can be used to facilitate government agencies' decision-making in land-use planning and environmental management, and for vegetation and biodiversity conservation. The information can also be used to assist land managers in the estimation of safe carrying capacities which will help to prevent overgrazing and land degradation.

An efficient and effective localization method for networked disjoint top-view cameras

Disjoint top-view networked cameras are among the most commonly utilized networks in many applications. One of the open questions for these cameras' study is the computation of extrinsic parameters (positions and orientations), named extrinsic calibration or localization of cameras. Current approaches either rely on strict assumptions of the object motion for accurate results or fail to provide results of high accuracy without the requirement of the object motion. To address these shortcomings, we present a location-constrained maximum a posteriori (LMAP) approach by applying known locations in the surveillance area, some of which would be passed by the object opportunistically. The LMAP approach formulates the problem as a joint inference of the extrinsic parameters and object trajectory based on the cameras' observations and the known locations. In addition, a new task-oriented evaluation metric, named MABR (the Maximum value of All image points' Back-projected localization errors' L2 norms Relative to the area of field of view), is presented to assess the quality of the calibration results in an indoor object tracking context. Finally, results herein demonstrate the superior performance of the proposed method over the state-of-the-art algorithm based on the presented MABR and classical evaluation metric in simulations and real experiments.

A sub‒domain smoothed Galerkin method for solid mechanics problems

A sub‒domain smoothed Galerkin method is proposed to integrate the advantages of mesh‒free Galerkin method and FEM. Arbitrarily shaped sub‒domains are predefined in problems domain with mesh‒free nodes. In each sub‒domain, based on mesh‒free Galerkin weak formulation, the local discrete equation can be obtained by using the moving Kriging interpolation, which is similar to the discretization of the high‒order finite elements. Strain smoothing technique is subsequently applied to the nodal integration of sub‒domain by dividing the sub‒domain into several smoothing cells. Moreover, condensation of DOF can also be introduced into the local discrete equations to improve the computational efficiency. The global governing equations of present method are obtained on the basis of the scheme of FEM by assembling all local discrete equations of the sub‒domains. The mesh‒free properties of Galerkin method are retained in each sub‒domain. Several 2D elastic problems have been solved on the basis of this newly proposed method to validate its computational performance. These numerical examples proved that the newly proposed sub‒domain smoothed Galerkin method is a robust technique to solve solid mechanics problems based on its characteristics of high computational efficiency, good accuracy, and convergence.