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.

Thromboxane synthase expression and correlation with VEGF and angiogenesis in non-small cell lung cancer

Background Thromboxane synthase (TXS) metabolizes prostaglandin H2 into thromboxanes, which are biologically active on cancer cells. TXS over-expression has been reported in a range of cancers, and associated with angiogenesis and poor outcome. TXS has been identified as a potential therapeutic target in NSCLC. This study examines a link between TXS expression, angiogenesis, and survival in NSCLC. Methods TXS and VEGF metabolite levels were measured in NSCLC serum samples (n=46) by EIA. TXB2 levels were correlated with VEGF. A 204-patient TMA was stained for TXS, VEGF, and CD-31 expression. Expression was correlated with a range of clinical parameters, including overall survival. TXS expression was correlated with VEGF and CD-31. Stable TXS clones were generated and the effect of overexpression on tumor growth and angiogenesis markers was examined in-vitro and in-vivo (xenograft mouse model). Results Serum TXB2 levels were correlated with VEGF (p<0.05). TXS and VEGF were expressed to a varying degree in NSCLC tissue. TXS was associated with VEGF (p<0.0001) and microvessel density (CD-31; p<0.05). TXS and VEGF expression levels were higher in adenocarcinoma (p<0.0001) and female patients (p<0.05). Stable overexpression of TXS increased VEGF secretion in-vitro. While no significant association with patient survival was observed for either TXS or VEGF in our patient cohort, TXS overexpression significantly (p<0.05) increased tumor growth in-vivo. TXS overexpression was also associated with higher levels of VEGF, microvessel density, and reduced apoptosis in xenograft tumors. Conclusion TXS promotes tumor growth in-vivo in NSCLC, an effect which is at least partly mediated through increased tumor angiogenesis.

Reluctantly virtual : modelling copyright industry dynamics

During the evolution of the music industry, developments in the media environment have required music firms to adapt in order to survive. Changes in broadcast radio programming during the 1950s; the Compact Cassette during the 1970s; and the deregulation of media ownership during the 1990s are all examples of changes which have heavily affected the music industry. This study explores similar contemporary dynamics, examines how decision makers in the music industry perceive and make sense of the developments, and reveals how they revise their business strategies, based on their mental models of the media environment. A qualitative system dynamics model is developed in order to support the reasoning brought forward by the study. The model is empirically grounded, but is also based on previous music industry research and a theoretical platform constituted by concepts from evolutionary economics and sociology of culture. The empirical data primarily consist of 36 personal interviews with decision makers in the American, British and Swedish music industrial ecosystems. The study argues that the model which is proposed, more effectively explains contemporary music industry dynamics than music industry models presented by previous research initiatives. Supported by the model, the study is able to show how “new” media outlets make old music business models obsolete and challenge the industry’s traditional power structures. It is no longer possible to expose music at one outlet (usually broadcast radio) in the hope that it will lead to sales of the same music at another (e.g. a compact disc). The study shows that many music industry decision makers still have not embraced the new logic, and have not yet challenged their traditional mental models of the media environment. Rather, they remain focused on preserving the pivotal role held by the CD and other physical distribution technologies. Further, the study shows that while many music firms remain attached to the old models, other firms, primarily music publishers, have accepted the transformation, and have reluctantly recognised the realities of a virtualised environment.

Development of a Remote Sensing Core Curriculum submitted for the sessions on educational initiatives in Geoscience and Remote Sensing

A Remote Sensing Core Curriculum (RSCC) development project is currently underway. This project is being conducted under the auspices of the National Center for Geographic Information and Analysis (NCGIA). RSCC is an outgrowth of the NCGIA GIS Core Curriculum project. It grew out of discussions begun at NCGIA, Initiative 12 (I-12): 'Integration of Remote Sensing and Geographic Information Systems'. This curriculum development project focuses on providing professors, teachers and instructors in undergraduate and graduate institutions with course materials from experts in specific subject matter for areas use in the class room.

The synthesis and structure of the symmetrical isomer of C5H-

The ion (C2CHC2)(-) is formed in the gas phase by the process -C=C-CH(OCOR)-C=CD --> (C2CHC2)(-) + ('RDCO2') [R = H, Me or Et]; the ground state structure is a singlet, with C-2 nu symmetry.

Factors affecting the extraction of absorbed dose information in a 3D polymer gel dosimeter by X ray computed tomography (IAEA-CN-96/122P)

Two sources of uncertainty in the X ray computed tomography imaging of polymer gel dosimeters are investigated in the paper.The first cause is a change in postirradiation density, which is proportional to the computed tomography signal and is associated with a volume change. The second cause of uncertainty is reconstruction noise.A simple technique that increases the residual signal to noise ratio by almost two orders of magnitude is examined.

Using a smartphone application for customer-centric banking

The banking industry is under pressure. In order to compete, banks should adapt to concentrating on the specific customer needs, following an outside-in perspective. This paper presents the design of a business model for banks that considers this development by providing flexible and comprehensive support for retail banking clients. It is demonstrated that the identification of customer processes and the consequent alignment of banking services to those processes implies great potential to increase customer retention in banking. It will be shown that information technology – especially smartphones – can serve as an interface between customer and suppliers to enable an alignment of offerings to customer processes. This approach enables the integration of banks into their customers’ lifestyle, creating emotional value added, improving the personal relationship and the customers’ affiliation with the bank. The paper presents the design of such a customer-process-centric smartphone application and derives success factors for implementation.

Framework of a process laboratory for the operational control of service processes

Service processes such as financial advice, booking a business trip or conducting a consulting project have emerged as units of analysis of high interest for the business process and service management communities in practice and academia. While the transactional nature of production processes is relatively well understood and deployed, the less predictable and highly interactive nature of service processes still lacks in many areas appropriate methodological grounding. This paper proposes a framework of a process laboratory as a new IT artefact in order to facilitate the holistic analysis and simulation of such service processes. Using financial services as an example, it will be shown how such a process laboratory can be used to reduce the complexity of service process analysis and facilitate operational service process control.

Formation of neutral C7H2 isomers from pour isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations \[E3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)\] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) \[(HC equivalent to C)(2)C=C=C\](-.) \[from the reaction between (HC equivalent to C)(3)COCH3 and HO- \], (ii) \[HC=C=C=C=C=C=CH\](-.) \[from the reaction between HC equivalent to C-C equivalent to C-CD(OH)-C equivalent to CH and HO-\], (iii) \[C=C=C=C=C=C=CH2\](-.) \[from the reaction between DC equivalent to C-C equivalent to C-C equivalent to C-CH2OCH2CH3 and HO-\], and (iv) \[C equivalent to C-CH2-C equivalent to C-C equivalent to C\](-.) \[from the bis desilylation reaction of (CH3)(3)Si-C equivalent to C-CH2-C equivalent to C-C equivalent to C-Si (CH3)(3)With SF6-.\]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10(-6) s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

Formation of neutral C7H2 isomers from four isomeric C7H2 radical anion precursors in the gas phase

Consideration of theoretical calculations [B3LYP/aug-cc-pVDZ//B3LYP/6-31G(d)] of the structures of ten C7H2 neutral isomers and the nine corresponding C7H2 radical anions have led us to synthesize four stable C7H2 radical anions in the ion source of our ZAB 2HF mass spectrometer, and to convert these to C7H2 neutrals. The four radical anion isomers prepared were (i) [(HC≡C)2C=C=C]-̇ [from the reaction between (HC≡C)3COCH3 and HO- ], (ii) [HC=C=C=C=C=C=CH]-̇ [from the reaction between HC≡C-C≡C- CD(OH)-C≡CH and HO-], (iii) [C=C=C=C=C=C=CH2]-̇ [from the reaction between DC≡C-C≡C- C≡C-CH2OCH2CH3 and HO-], and (iv) [C≡C-CH2-C≡C-C≡C]-̇ [from the bis desilylation reaction of (CH3)3Si-C≡C-CH2-C≡C-C≡C-Si (CH3)3 with SF6 -̇]. The four anions were further characterized by their collisional activation (negative ion) and charge reversal (CR, positive ion) mass spectra. The anions were converted into their corresponding neutrals by charge stripping, and the correspondence between the charge reversal (CR) and neutralization reionization (-NR+) mass spectra of each anion is taken as evidence that within the time frame of the -NR+ experiment (some 10-6 s), each neutral is stable and undergoes no major rearrangement or interconversion to a more stable isomer. Theory and experiment are in accord for these systems.

A biomechanical analysis of growing rods used in the management of early onset scoliosis

INTRODUCTION Managing spinal deformities in young children is challenging, particularly early onset scoliosis (EOS). Surgical intervention is often required if EOS has been unresponsive to conservative treatment particularly with rapidly progressive curves. An emerging treatment option for EOS is fusionless scoliosis surgery. Similar to bracing, this surgical option potentially harnesses growth, motion and function of the spine along with correcting spinal deformity. Dual growing rods are one such fusionless treatment, which aims to modulate growth of the vertebrae. The aim of this study was to ascertain the extent to which semiconstrained growing rods (Medtronic, Sofamor, Danek, Memphis, TN) with a telescopic sleeve component, reduce rotational constraint on the spine compared with standard "constrained / rigid" rods and hence potentially provide a more physiological mechanical environment for the growing spine. METHODS Six 40-60kg English Large White porcine spines served as a model for the paediatric human spine. Each spine was dissected into a 7 level thoracolumbar multi-segment unit (MSU), removing all non-ligamentous soft tissues and leaving 3cm of ribs either side. Pure nondestructive axial rotation moments of ±4Nm at a constant rotation rate of 8deg.s-1 were applied to the mounted MSU spines using a biaxial Instron testing machine. Displacement of each vertebral level was captured using a 3D motion tracking system (Optotrak 3020, Northern Digital Inc, Waterloo, ON). Each spine was tested in an un-instrumented state first and then with appropriately sized semi-constrained growing rods and rigid rods in alternating sequence. The rods were secured by multi-axial pedicle screws (Medtronic CD Horizon) at levels 2 and 6 of the construct. The range of motion (ROM), neutral zone (NZ) size and stiffness (Nm.deg-1) were calculated from the Instron load-displacement data and intervertebral ROM was calculated through a MATLAB algorithm from Optotrak data. RESULTS Irrespective of the order of testing, rigid rods significantly reduced the total ROM compared with semi-constrained rods (p<0.05) with in a significantly stiffer spine for both left and right axial rotation (p<0.05). Analysing the intervertebral motion within the instrumented levels 2-6, rigid rods showed reduced ROM compared with semi-constrained growing rods and compared with un-instrumented motion segments. CONCLUSION Semi-constrained growing rods maintain similar stiffness in axial rotation to un-instrumented spines, while dual rigid rods significantly reduce axial rotation. Clinically the effect of semi-constrained growing rods as observed in this study is that they would be expected to allow growth via the telescopic rod components while maintaining the axial flexibility of the spine, which may reduce occurrence of the crankshaft phenomenon.

Multiband photoluminescence from carbon nanoflakes synthesized by hot filament CVD: towards solid-state white light sources

Carbon nanoflakes (CNFLs) are synthesized on silicon substrates deposited with carbon islands in a methane environment using hot filament chemical vapor deposition. The structure and composition of the CNFLs are studied using field emission scanning electron microscopy, high-resolution transmission electron microscopy, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy. The results indicate that the CNFLs are composed of multilayer graphitic sheets and the area and thickness of CNFs increase with the growth time. The photoluminescence (PL) of CNFLs excited by a 325 nm He-Cd laser exhibits three strong bands centered at 408, 526, and 699 nm, which are related to the chemical radicals terminated on the CNFLs and the associated interband transitions. The PL results indicate that the CNFLs are promising as an advanced nano-carbon material capable of generating white light emission. These outcomes are significant to control the electronic structure of CNFLs and contribute to the development of next-generation solid-state white light emission devices. © 2014 the Partner Organisations.

From nucleation to nanowires : a single-step process in reactive plasmas

This feature article introduces a deterministic approach for the rapid, single-step, direct synthesis of metal oxide nanowires. This approach is based on the exposure of thin metal samples to reactive oxygen plasmas and does not require any intervening processing or external substrate heating. The critical roles of the reactive oxygen plasmas, surface processes, and plasma-surface interactions that enable this growth are critically examined by using a deterministic viewpoint. The essentials of the experimental procedures and reactor design are presented and related to the key process requirements. The nucleation and growth kinetics is discussed for typical solid-liquid-solid and vapor-solid-solid mechanisms related to the synthesis of the oxide nanowires of metals with low (Ga, Cd) and high (Fe) melting points, respectively. Numerical simulations are focused on the possibility to predict the nanowire nucleation points through the interaction of the plasma radicals and ions with the nanoscale morphological features on the surface, as well as to control the localized 'hot spots' that in turn determine the nanowire size and shape. This generic approach can be applied to virtually any oxide nanoscale system and further confirms the applicability of the plasma nanoscience approaches for deterministic nanoscale synthesis and processing.

Reactive oxygen plasma-enabled synthesis of nanostructured CdO : tailoring nanostructures through plasma–surface interactions

Plasma-assisted synthesis of nanostructures is one of the most precise and effective approaches used in nanodevice fabrication. Here we report on the innovative approach of synthesizing nanostructured cadmium oxide films on Cd substrates using a reactive oxygen plasma-based process. Under certain conditions, the surface morphology features arrays of crystalline CdO nano/micropyramids. These nanostructures grow via unconventional plasma-assisted oxidation of a cadmium foil exposed to inductively coupled plasmas with a narrow range of process parameters. The growth of the CdO pyramidal nanostructures takes place in the solid-liquid-solid phase, with the rates determined by the interaction of plasma-produced oxygen atoms and ions with the surface. It is shown that the size of the pyramidal structures can be effectively controlled by the fluxes of oxygen atoms and ions impinging on the cadmium surface. The unique role of the reactive plasma environment in the controlled synthesis of CdO nanopyramidal structures is discussed as well.

Determinants of second row passenger comfort

China is becoming an increasingly important automotive market. Customer’s vehicle usage, preferences and requirements differ from traditional western markets in a number of aspects – rear seat usage rates are higher, vehicles are used for business purposes as well as for private transport and rear seat usage is generally more important to Chinese customers compared to their western counterparts. The purpose of this project is to dimension and investigate these differences from an ergonomics perspective and use these results to guide the design of future products. The focus for this project will be specific to vehicles in the CD segment. More specifically, this project focuses on the second row ‘ambience’. Ambience refers to the global feeling perceived by second row passengers, and the main factors contributing to ambience are: ingress and egress comfort, seat comfort, roominess, and ease of use of the controls. In order to investigate the aforementioned parameters, an experimental study has been conducted in Shanghai, China. This experiment involved 80 healthy Chinese CD- and D-car customers. These subjects were asked to evaluate different features present in the second row environment of three different cars: A Ford Mondeo, Toyota Camry and Mercedes S-class. Various data has been collected during this experiment: First, the anthropometric dimensions of the subjects have been measured. The subjects were also asked to fill a questionnaire about demographics, their own car usage, and their perception of a various number of features present in the three tested cars. A great amount of technical data was also collected. The first part of this report presents the results given by the questionnaires. It includes Chinese demographics, vehicle usage habits, and the subjective perception of the features present in the tested cars. It also presents the results of the anthropometric measurements. This gives a first insight into Chinese customers’ habits and preferences. The second part deals with the technical data recorded during the experiment: second row seat adjustment ranges, roominess, optimal location of controls, and pressure mapping analysis. Analysis of technical data allows a deeper understanding of the factors contributing to comfort and ambience perception. Using the technical data together with the comfort ratings given by the subjects in the questionnaire, recommendations on several design parameters were provided. Finally, an experimental study of car ingress-egress has been conducted in a University laboratory controlled environment. During this study, the ingress and egress motion of 20 customers from Chinese origin was recorded using a motion capture system. The last part of this report presents the protocol and data processing that led to building an ingress-egress motion database that was provided to Ford.