Molecular Heterojunctions of Oligo(phenylene ethynylene)s with Linear to Cruciform Framework

Electrical transport properties of molecular junctions are fundamentally affected by the energy alignment between molecular frontier orbitals (highest occupied molecular orbital (HOMO) or lowest unoccupied molecular orbital (LUMO)) and Fermi level (or work function) of electrode metals. Dithiafulvene (DTF) is used as substituent group to the oligo(phenylene ethynylene) (OPE) molecular wires and different molecular structures based on OPE3 backbone (with linear to cruciform framework) are achieved, with viable molecular orbitals and HOMO–LUMO energy gaps. OPE3, OPE3–DTF, and OPE3–tetrathiafulvalene (TTF) can form good self‐assembled monolayers (SAMs) on Au substrates. Molecular heterojunctions based on these SAMs are investigated using conducting probe–atomic force microscopy with different tips (Ag, Au, and Pt) and Fermi levels. The calibrated conductance values follow the sequence OPE3–TTF > OPE3–DTF > OPE3 irrespective of the tip metal. Rectification properties (or diode behavior) are observed in case of the Ag tip for which the work function is furthest from the HOMO levels of the OPE3s. Quantum chemical calculations of the transmission qualitatively agree with the experimental data and reproduce the substituent effect of DTF. Zero‐bias conductance, and symmetric or asymmetric couplings to the electrodes are investigated. The results indicate that improved fidelity of molecular transport measurements may be achieved by systematic studies of homologues series of molecular wires applying several different metal electrodes.     

Towards garden city wonderlands: new town planning in 1950s Taiwan

This article explores the historical context, process and result of introducing and implementing ‘new’ town planning in early post‐war Taiwan. The two so‐called ‘garden cities’ are examined: Jhong‐Sing New Village and Yonghe City, both of which were formulated in the mid‐1950s by the same group of local planners. It reveals that the assumed necessity of importing Western planning paradigms arose from the abrupt escalation of urban concentration caused by the late 1940s mass migrations from China. To cope with this unprecedented population growth, planning profession was swiftly established. The novice planners, in search of a reference for developing ‘new’ towns to decentralise excessive urbanisation, modelled their ‘new’ town planning on English suburban morphology. In the absence of an input of external expertise, the planners appeared to mistake aesthetic order and pastoral imagery of low‐density residential development in England as practically viable solutions to the pressing urban problems in Taiwan. In a false hope that adopting Western ideas and practices would quickly lead the island to a better world, Taiwan initiated the importation of planning paradigms. This planning transfer not only evidently manifests a mode of ‘borrowing’ in post‐colonial countries in international diffusion but also re‐articulates the disseminating nature of modern planning and the existence of one‐direction flows characterising the global dynamics of diffusion in the twentieth century.     

International influences and professional rivalry in early Danish planning

Influences on early Danish planning came from a variety of international sources. The Big City paradigm was mainly taken over from German planning, sometimes varied with elements from Haussmann and American cities. Later inspiration from Camillo Sitte and from the English Garden City movement was combined with traditional Danish small town values into a competing paradigm. The engineers mainly adhered to the Big City paradigm, whilst the architects were the chief proponents of the English inspiration, and these two paradigms have been used as tools of rivalry between the two professions. This discord might in the long run have led to a weakening of the planners’ political influence.     

Young adults and the decline of the urban English pub: issues for planning

The numbers of English public houses or “pubs” have reduced significantly in the last two decades. Politicians have called on the planning system to resist their closure but, at the same time, demand further controls over high-street bars. This paper explores the reasons for the decline and the rationale for supporting the continuation of the “traditional” English pub. Using evidence drawn from a wider study of the relationships between places and youth drinking cultures, the paper discusses young adults' use of pubs. While recognising the adverse effects of heavy drinking, arguments are put forward in support of the traditional pub as a site for restrained and responsible social interaction for young adults. The paper discusses the issues this raises for the UK planning system in the context of responsibilities for social sustainability and public health.     

Synthesis and Crystal Structure Characterization of Oxysilicate Apatites for Stabilization of Sr and Rare‐Earth Elements

Strontium (Sr) containing rare‐earth oxysilicate apatite A^I₄A^II₆(SiO₄)₆O₂ is considered a good matrix to accommodate radionuclide as its cation sites can incorporate lanthanide elements other than Sr. Here, we report a study on the synthesis of Nd₈Sr₂(SiO₄)₆O₂ and Yb₈Sr₂(SiO₄)₆O₂, which adopt P6₃/m apatite symmetry, as well as the characterization of crystallographic structures using X‐ray diffraction and electron microscopy. It is found that A^I position is shared by Nd, Yb and Sr, and A^IO₆ polyhedra are face‐connected, forming column structures, which are linked to SiO₄ tetrahedra, creating continuous channels. The Rietveld refinement shows that Nd and Yb prefer the A^II position in the channel. The twisted angle of adjacent triangle faces in an A^I‐O polyhedron along [001] is a critical parameter to identify the channel volume and its value varies when different cations are incorporated. The twisted angles for Nd‐apatite and Yb are 24.2° and 22.7° The findings provide a new insight into nuclear waste stabilization by apatite‐type structure.     

Tailoring the properties of deposited thin coating and print features in flexography by application of UV-ozone treatment

Printed functional materials are a rapidly growing area of interest for low-cost high-speed device manufacture with flexographic printing seen as a route to achieving this. The relationship between surface tension of the ink and surface free energy (SFE) of the photopolymer plate is a key for optimum performance. However, traditional methods of surface tension modification of the ink/coating often cannot be employed for functional inks. In this research, rapid, permanent modification of flexographic printing plate’s SFE is achieved through controlled UV-ozone treatment, and the effects of the treatment on the polar and dispersive component of SFE are analyzed by Fourier transform infrared attenuated total reflectance spectroscopy, swelling experiments, and roughness measurements. Printing trials using the modified printing plates reveal improved print uniformity and control of deposited ink layer thickness, as well as improved print features—particularly track and pad junctions which can be problematic for printed electronic applications. The ability to rapidly tailor printing plate SFE is of benefit to all volume printing applications. Furthermore, it is of critical importance for functional printing and printed electronics where surface tension of the ink is determined by the functional material and chemical modification is not possible or desirable.     

Tracking the Molecular Fingerprint of Head and Neck Cancer for Recurrence Detection in Liquid Biopsies

The 5-year relative survival for patients with head and neck cancer, the seventh most common form of cancer worldwide, was reported as 67% in developed countries in the second decade of the new millennium. Although surgery, radiotherapy, chemotherapy, or combined treatment often elicits an initial satisfactory response, relapses are frequently observed within two years. Current surveillance methods, including clinical exams and imaging evaluations, have not unambiguously demonstrated a survival benefit, most probably due to a lack of sensitivity in detecting very early recurrence. Recently, liquid biopsy monitoring of the molecular fingerprint of head and neck squamous cell carcinoma has been proposed and investigated as a strategy for longitudinal patient care. These innovative methods offer rapid, safe, and highly informative genetic analysis that can identify small tumors not yet visible by advanced imaging techniques, thus potentially shortening the time to treatment and improving survival outcomes. In this review, we provide insights into the available evidence that the molecular tumor fingerprint can be used in the surveillance of head and neck squamous cell carcinoma. Challenges to overcome, prior to clinical implementation, are also discussed.     

Predicting shrinkage and warpage of fiber-reinforced composite parts

One major problem that arises in the design of plastic parts, especially those that are fiber reinforced, is the change of shape and dimension as a result of shrinkage and warpage. These material inhomogeneities are caused by flowinduced fiber orientation, curing, poor thermal mold lay-out, and other processing conditions. This paper presents a simulation that predicts shirnkage and warpage of 3-D compression molded fiber reinforced composite parts. The simulation represents the structure with the 3-noded shell elements used in mold filling simulations. The calculated results indicate that fiber orientation strongly affect the final properties, which vary with different chage locations, have a significant effect on warpage. Unsymmetric curing, caused by uneven mold temperatures, could lead to a thermal moment that could possibly help reduce warpage.