Frequency spectroscopy of irreversible electrochemical nucleation kinetics on the nanoscale

An approach is developed for probing the thermodynamics and kinetics of irreversible electrochemical reactions on solid surfaces based on local frequency-voltage spectroscopy. For a model Li-ion conductor surface, two regimes for bias-controlled behavior are demonstrated and ascribed to the difference in the critical nucleus size. The electrostatic and electrochemical phenomena at the tip-surface junction are analyzed. These studies suggest an experimental pathway for exploring local electrochemical activity in solids.

Facile synthesis of thiol-functionalized amphiphilic polylactide–methacrylic diblock copolymers

Biodegradable amphiphilic diblock copolymers based on an aliphatic ester block and various hydrophilic methacrylic monomers were synthesized using a novel hydroxyl-functionalized trithiocarbonate-based chain transfer agent. One protocol involved the one-pot simultaneous ring-opening polymerization (ROP) of the biodegradable monomer (3S)-cis-3,6-dimethyl-1,4-dioxane-2,5-dione (L-lactide, LA) and reversible addition–fragmentation chain transfer (RAFT) polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) or oligo(ethylene glycol) methacrylate (OEGMA) monomer, with 4-dimethylaminopyridine being used as the ROP catalyst and 2,2′-azobis(isobutyronitrile) as the initiator for the RAFT polymerization. Alternatively, a two-step protocol involving the initial polymerization of LA followed by the polymerization of DMA, glycerol monomethacrylate or 2-(methacryloyloxy)ethyl phosphorylcholine using 4,4′-azobis(4-cyanovaleric acid) as a RAFT initiator was also explored. Using a solvent switch processing step, these amphiphilic diblock copolymers self-assemble in dilute aqueous solution. Their self-assembly provides various copolymer morphologies depending on the block compositions, as judged by transmission electron microscopy and dynamic light scattering. Two novel disulfide-functionalized PLA-branched block copolymers were also synthesized using simultaneous ROP of LA and RAFT copolymerization of OEGMA or DMA with a disulfide-based dimethacrylate. The disulfide bonds were reductively cleaved using tributyl phosphine to generate reactive thiol groups. Thiol–ene chemistry was utilized for further derivatization with thiol-based biologically important molecules and heavy metals for tissue engineering or bioimaging applications, respectively.

Spatial statistics to estimate peat thickness using airborne radiometric data

Soil carbon stores are a major component of the annual returns required by EU governments to the Intergovernmental Panel on Climate Change. Peat has a high proportion of soil carbon due to the relatively high carbon density of peat and organic-rich soils. For this reason it has become increasingly important to measure and model soil carbon stores and changes in peat stocks to facilitate the management of carbon changes over time. The approach investigated in this research evaluates the use of airborne geophysical (radiometric) data to estimate peat thickness using the attenuation of bedrock geology radioactivity by superficial peat cover. Remotely sensed radiometric data are validated with ground peat depth measurements combined with non-invasive geophysical surveys. Two field-based case studies exemplify and validate the results. Variography and kriging are used to predict peat thickness from point measurements of peat depth and airborne radiometric data and provide an estimate of uncertainty in the predictions. Cokriging, by assessing the degree of spatial correlation between recent remote sensed geophysical monitoring and previous peat depth models, is used to examine changes in peat stocks over time. The significance of the coregionalisation is that the spatial cross correlation between the remote and ground based data can be used to update the model of peat depth. The result is that by integrating remotely sensed data with ground geophysics, the need is reduced for extensive ground-based monitoring and invasive peat depth measurements. The overall goal is to provide robust estimates of peat thickness to improve estimates of carbon stocks. The implications from the research have a broader significance that promotes a reduction in the need for damaging onsite peat thickness measurement and an increase in the use of remote sensed data for carbon stock estimations.

Transnational connections in European crime film series (1908–1914)

This article addresses the issue of ‘European popular cinema’ by discussing a very specific phenomenon, i.e. the crime series produced in the years immediately preceding World War I (e.g. Victorin Jasset’s Nick Carter, Viggo Larsen’s Arsène Lupin contra Sherlock, Ubaldo Maria del Colle’s Raffles, il ladro misterioso, Louis Feuillade’s Fantômas, George Pearson’s Ultus). On the one hand, the transnational circulation of these films is seen as the result of the development of the European cultural industries since the late nineteenth century; on the other hand, the rapid decline of this genre testifies of the historical peculiarity of this production. In particular, the popular heroic figure of the ‘gentleman thief’ seems to express at the same time the liberating, anti-hierarchial ethos of modernization and the dream of a quiet conciliation of the new and the traditional values: as a consequence, it might be regarded as a telling example of the economical, social and ideological transformations of that crucial phase in European history, when the development of the second industrial revolution and the first phase of ‘globalization’ pointed at the birth of a supranational sphere before the outbreak of World War I, which would temporarily stop this process.

Further refinement of the nature of the communication impairment in Cornelia de Lange syndrome

Purpose – Research into the communication skills of individuals with Cornelia de Lange syndrome (CdLS) is extremely limited. This paper aims to evaluate the nature of these skills and impairments in CdLS using a detailed informant assessment of pre-verbal communication skills.
Design/methodology/approach – The study used the Pre-verbal Communication Schedule to evaluate communication skills in individuals with CdLS (n ¼ 14), aged five to14 years. The group was compared with a contrast group of individuals with Cri du Chat syndrome (CdCS; n ¼ 14) who were matched for age and intellectual ability.
Findings – A significant difference was identified in understanding non-vocal communication (p , 0.005), with the CdLS group showing a greater deficit. These findings indicate the presence of a syndrome-specific deficit in understanding non-verbal communication in individuals with CdLS and suggest that there may be a dissociation between the processing of verbal and non-verbal communication.
Originality/value – The findings indicate that, in many ways, these two syndrome groups are not dissimilar in terms of their communication skills. However, individuals with CdLS show a syndrome-specific deficit in understanding non-vocal communication relative to the CdCS group.

Thermotropic phase boundaries in classic ferroelectrics

High-performance piezoelectrics are lead-based solid solutions that exhibit a so-called morphotropic phase boundary, which separates two competing phases as a function of chemical composition; as a consequence, an intermediate low-symmetry phase with a strong piezoelectric effect arises. In search for environmentally sustainable lead-free alternatives that exhibit analogous characteristics, we use a network of competing domains to create similar conditions across thermal inter-ferroelectric transitions in simple, lead-free ferroelectrics such as BaTiO 3 and KNbO 3. Here we report the experimental observation of thermotropic phase boundaries in these classic ferroelectrics, through direct imaging of low-symmetry intermediate phases that exhibit large enhancements in the existing nonlinear optical and piezoelectric property coefficients. Furthermore, the symmetry lowering in these phases allows for new property coefficients that exceed all the existing coefficients in both parent phases. Discovering the thermotropic nature of thermal phase transitions in simple ferroelectrics thus presents unique opportunities for the design of 'green' high-performance materials.

The value of water quality improvements in the region Berlin-Brandenburg as a function of distance and state residency

This study uses a discrete choice experiment (DCE) to elicit willingness to pay estimates for changes in the water quality of three rivers. As many regions the metropolitan region Berlin-Brandenburg struggles to achieve the objectives of the Water Framework Directive until 2015. A major problem is the high load of nutrients. As the region is part of two states (Länder) and the river sections are common throughout the whole region we account for the spatial context twofold. Firstly, we incorporate the distance between each respondent and all river stretches in all MNL and RPL models, and, secondly, we consider whether respondents reside in the state of Berlin or Brandenburg. The compensating variation (CV) calculated for various scenarios shows that overall people would significantly benefit from improved water quality. The CV measures, however, also reveal that not considering the spatial context would result in severely biased welfare measures. While the distance decay effect lowers CV, state residency is connected to the frequency of status quo choices and not accounting for residency would underestimate possible welfare gains in one state. Another finding is that the extent of the market varies with respect to attributes (river stretches) and attribute levels (water quality levels).

Probing charge screening dynamics and electrochemical processes at the solid–liquid interface with electrochemical force microscopy

The presence of mobile ions complicates the implementation of voltage-modulated scanning probe microscopy techniques such as Kelvin probe force microscopy (KPFM). Overcoming this technical hurdle, however, provides a unique opportunity to probe ion dynamics and electrochemical processes in liquid environments and the possibility to unravel the underlying mechanisms behind important processes at the solid–liquid interface, including adsorption, electron transfer and electrocatalysis. Here we describe the development and implementation of electrochemical force microscopy (EcFM) to probe local bias- and time-resolved ion dynamics and electrochemical processes at the solid–liquid interface. Using EcFM, we demonstrate contact potential difference measurements, consistent with the principles of open-loop KPFM operation. We also demonstrate that EcFM can be used to investigate charge screening mechanisms and electrochemical reactions in the probe–sample junction. We further establish EcFM as a force-based imaging mode, allowing visualization of the spatial variability of sample-dependent local electrochemical properties.

TBX2 represses CST6 resulting in uncontrolled legumain activity to sustain breast cancer proliferation: a novel cancer-selective target pathway with therapeutic opportunities.

TBX2 is an oncogenic transcription factor known to drive breast cancer proliferation. We have identified the cysteine protease inhibitor Cystatin 6 (CST6) as a consistently repressed TBX2 target gene, co-repressed through a mechanism involving Early Growth Response 1 (EGR1). Exogenous expression of CST6 in TBX2-expressing breast cancer cells resulted in significant apoptosis whilst non-tumorigenic breast cells remained unaffected. CST6 is an important tumor suppressor in multiple tissues, acting as a dual protease inhibitor of both papain-like cathepsins and asparaginyl endopeptidases (AEPs) such as Legumain (LGMN). Mutation of the CST6 LGMN-inhibitory domain completely abrogated its ability to induce apoptosis in TBX2-expressing breast cancer cells, whilst mutation of the cathepsin-inhibitory domain or treatment with a pan-cathepsin inhibitor had no effect, suggesting that LGMN is the key oncogenic driver enzyme. LGMN activity assays confirmed the observed growth inhibitory effects were consistent with CST6 inhibition of LGMN. Knockdown of LGMN and the only other known AEP enzyme (GPI8) by siRNA confirmed that LGMN was the enzyme responsible for maintaining breast cancer proliferation. CST6 did not require secretion or glycosylation to elicit its cell killing effects, suggesting an intracellular mode of action. Finally, we show that TBX2 and CST6 displayed reciprocal expression in a cohort of primary breast cancers with increased TBX2 expression associating with increased metastases. We have also noted that tumors with altered TBX2/CST6 expression show poor overall survival. This novel TBX2-CST6-LGMN signaling pathway, therefore, represents an exciting opportunity for the development of novel therapies to target TBX2 driven breast cancers.

Sustainable Technoscientific Development and the Innovator Citizen

Sustainable development could provide a critical foil for individual
and especially collective reflection on the normative
direction, ends and means employed by societies, particularly
around the economy, its technology and resource-intensive
orientation and configuration with ecosystems. However,
although sustainable development is a constitutional objective
of the EU, its implementation in strategies and policies reveals
a much narrower meaning. By framing sustainable development
as ecological modernisation on the basis of technoscientific
innovation, and by imagining citizens as entrepreneurs in a
knowledge-based European economy, openings for democratic
experimentation and social innovation are limited and even
forestalled. In addition, the disruptive and transformational
potential of citizenship is stymied. Still, sustainable development
has resonance within citizenship and human rights
discourses that provide important resources for the fashioning
of common understanding. These are valuable supplements to
the repertoire of European citizenship that could help to embed
sustainable development in the social fabric and generate
alternative imaginaries and futures of a sustainable Europe.

Endothelial progenitor cells in diabetic retinopathy

Diabetic retinopathy (DR) is a leading cause of visual impairment worldwide. Patients with DR may irreversibly lose sight as a result of the development of diabetic macular edema (DME) and/or proliferative diabetic retinopathy (PDR); retinal blood vessel dysfunction and degeneration plays an essential role in their pathogenesis. Although new treatments have been recently introduced for DME, including intravitreal vascular endothelial growth factor inhibitors (anti-VEGFs) and steroids, a high proportion of patients (~40-50%) do not respond to these therapies. Furthermore, for people with PDR, laser photocoagulation remains a mainstay therapy despite this being an inherently destructive procedure. Endothelial progenitor cells (EPCs) are a low-frequency population of circulating cells known to be recruited to sites of vessel damage and tissue ischemia where they promote vascular healing and re-perfusion. A growing body of evidence suggests that the number and function of EPCs are altered in patients with varying degrees of diabetes duration, metabolic control, and in the presence or absence of DR. Although there are no clear-cut outcomes from these clinical studies, there is mounting evidence that some EPC sub-types may be involved in the pathogenesis of DR and may also serve as biomarkers for disease progression and stratification. Moreover, some EPC sub-types have considerable potential as therapeutic modalities for DME and PDR in the context of cell therapy. This study presents basic clinical concepts of DR and combines this with a general insight on EPCs and their relation to future directions in understanding and treating this important diabetic complication.

Micromaser spectrum and phase diffusion dynamics

We discuss a scheme to relate the phase diffusion dynamics of the micromaser field to the measured atomic population statistics. This can allow us to measure the linewidth of the micromaser spectrum and to solve a relevant decoherence problem in cavity quantum electrodynamics. The main steps are (i) a suitable preparation of the cavity field state to generate coherences, (ii) the transfer of information on the dynamics of field coherences to probe atoms by the action of an external resonant coherent field and (iii) the derivation of the phase diffusion rate, hence the micromaser linewidth, from the measured population statistics of the probe atoms. The method can be applied even in the presence of trapping states, where peculiar linewidth oscillations are expected for increasing pump rate, due to the quantum nature of the micromaser field.

A functional role of the sky’s polarization pattern for orientation in the greater mouse-eared bat

Animals can call on a multitude of sensory information to orient and navigate. In some cases they may calibrate these cues against each other to establish the most accurate information available. One such cue is the pattern of polarized light in the sky, which may be used as a geographical reference to calibrate other cues in the compass mechanism. Mammals, however, have not been shown to use this cue, even though they do calibrate a magnetic compass with sunset. In this paper we demonstrate that bats use polarization cues at sunset to calibrate a magnetic compass, subsequently used for orientation during a homing experiment. It is thus the only mammal known so far to make use of the polarization pattern in the sky. This is an intriguing finding as currently there is no clear understanding of how this cue is perceived in this taxon and has general implications for the sensory biology of mammalian vision.

Recent contribution of sediments and fluids to the mantle's volatile budget

Subduction modifies the cycling of Earth's volatile elements. Fluid-rich sediments and hydrated oceanic lithosphere enter the convecting mantle at subduction zones. Some of the sediments and volatile components are released from the subducting slab, promote mantle melting and are returned to the surface by volcanism. The remainder continue into the deeper mantle. Quantification of the fate of these volatiles requires an understanding of both the nature and timing of fluid release and mantle melting(1). Here we analyse the trace element and isotopic geochemistry of fragments of upper mantle rocks that were transported to the surface by volcanic eruptions above the Batan Island subduction zone, Philippines. We find that the mantle fragments exhibit extreme disequilibrium between their U-Th-Ra isotopic ratios, which we interpret to result from the interaction of wet sediment melts and slab-derived fluids with rocks in the overlying mantle wedge. We infer that wet sediments were delivered from the slab to the mantle wedge between 8,000 and 10,000 years ago, whereas aqueous fluids were delivered separately much later. We estimate that about 625 ppm of water is retained in the wedge. A significant volume of water could therefore be delivered to the mantle transition zone at the base of the upper mantle, or even to the deeper mantle.