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In this short essay, the focus is on social and political aspects of forced migration. It is argued that policies designed to restrict access to developed countries have, rather like the American “prohibition”, produced a thriving criminal market for smugglers, in this case of people. Making travel more difficult increases both their profits and the sophistication of their methods. Provision of targeted, properly controlled, support for refugees in countriesneighbouring conflict zones might help to reduce the pressure on travel to Europe and could be both more successful and more humanitarian. For those who do reach developed countries, there is scope to improve the legal decision-making process. Psychologicalinput should include scientific investigation of legal assumptions, and the provision of relevant expert literature reviews, for exampleconcerning modern knowledge of memory. Trust is the first casualty of repressive violence, and mistrust among opposition groups is probably one of the key mechanisms of its success. We need to make sure that we do not provide further grounds for this sort of reaction. Although there is no brave or new world ahead, we must continue to confront ignorance and prejudice, as we seek to avoid more humanitarian disasters. It is now just over thirty years since we published a potential framework for understanding how survivors of organised state violence react to complex and severe trauma (Turner & Gorst-Unsworth, 1990). We argued that no single psychological process underpins the reactions to this experience, and therefore, there can be no unitary torture syndrome, but rather a series of understandable psychological pathways activated to varying degrees by different experiences, leading to diversity of emotional response, with implications for recovery and treatment. We also asked family doctors about health needs of refugees (Ramsay & Turner, 1993), and it is wonderful to see how the evidence on treatment options has developed since then, especially in recent years. In this paper, looking back over the last thirty years, in celebration of the anniversary of Torture journal, I will focus on political, legal and forensic aspects of forced migration.

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e18694 Background: PIK3CA mutations seen in cancer also drive other disease, exciting interest in repurposing oncology therapies for non-oncology indications. ALP is a PI3Kα inhibitor approved for HR+, HER2– ABC with fulvestrant. Clinical benefit of ALP in PROS, a group of rare phenotypically varied disorders driven by mutations in PIK3CA, was found in 19 pts (Venot, 2018). EPIK-P1 (NCT04285723) collected real-world data (RWD) to confirm ALP’s efficacy and safety in PROS. In the primary analysis of the primary endpoint, 12/32 pts (37.5%; 95% CI, 21.1-56.3%) with complete cases responded (≥20% reduction in the sum of target lesion volume from index/treatment [tx] start). Adverse events (AEs) and tx-related AEs were experienced by 82.5% (n = 47) and 38.6% (n = 22) of pts, respectively. The most common tx-related AE was hyperglycemia (n = 7, 12.3%). No deaths were reported (Canaud, ESMO 2021 LBA23). Methods: EPIK-P1 retrospectively abstracted data from the medical charts of pts aged ≥2 y with PROS experiencing severe/life-threatening conditions receiving ALP under compassionate use. Secondary endpoints evaluated safety and clinical benefit. Results: 57 pts were enrolled and followed for a median of 18.1 mo. No pt in the primary analysis (complete cases, n = 32) had progressive disease (PD) at wk 24; 1 pt discontinued ALP prior to wk 24 and considered a nonresponder. Of the 12 responders, median duration of response (time from first documented response to first documented PD or death due to any cause) was not estimable. Median time to censoring (date of last adequate lesion assessment) was 63.3 wk (̃14.6 mo; range, 1 d-186.7 wk); 2 pts had no further imaging assessments, 10 pts did not experience an event and tx was ongoing at data cutoff. Time to censoring was > 6 mo in 7 pts and > 12 mo in 6 pts. 11/20 nonresponders (55.0%) had target lesion volume reduction ranging from 0.7 to 19.6%. No pt required rescue surgery between index and wk 24. At index all pts reported ≥1 PROS-related symptom (eg, fatigue, pain). At wk 24, 82.5% (n = 47) reported symptom improvement regardless of primary analysis response status (responders, 10/12, 83.3%; nonresponders, 16/20, 80.0%). Median daily dose was 50 mg for pediatrics and 250 mg for adults. Dose reductions or interruptions were experienced by 15.8% of pts (n = 9); AEs led to dose reductions and interruptions in 3.5% (n = 2) and 10.5% (n = 6) of pts, respectively. 52 pts (91.2%) remained on tx at data cutoff; among 5 pts (8.8%) who discontinued, pt decision was the leading cause. Conclusions: RWD from EPIK-P1 demonstrate alpelisib as well tolerated, providing clinical benefit to pts with PROS regardless of response status in the primary analysis of the primary endpoint. Continued RWD collection complements planned prospective, randomized, placebo-controlled studies, facilitating access to alpelisib as an emerging pharmacologic option for PROS. Clinical trial information: NCT04285723.

e18707 Background: PROS is a group of rare disorders driven by activating mutations in PIK3CA. Overactivation of the PI3K pathway, which regulates growth and proliferation, results in asymmetric malformations/overgrowths. Localized interventions are often not curative and no medical therapy for PROS is approved; however, mTOR inhibitors (ie sirolimus) are used off-label with modest success. Using a patient (pt)-focused approach, we seek to better understand the current path to diagnosis (dx), course of disease, interventions, and pt outcomes to optimize future therapies. Methods: Pts treated in the US are being actively recruited via interactions with pt advocacy groups, pt communities, social media, and allstripes.com. Following research and HIPAA authorization from each pt/guardian, AllStripes’ proprietary real-world evidence (RWE) platform collects pt medical records into a master medical record from which study data are abstracted. All activities are covered under AllStripes’ IRB-approved protocol. To enroll in the PROS cohort, pts must have a confirmed PROS dx via PIK3CA genetic testing. Data completeness and nomenclature are dependent on physician documentation. Results: To date 14 pts (7 female, 7 male) have enrolled; median age at enrollment was 10.5 y (range, 1-38). Of the 14 pts, 71.4% of pts (n = 10) had congenital onset. PIK3CA genetic testing was primarily (n = 12, 85.7%) completed as a part of a multigene panel. The most frequent specialties involved in dx were medical genetics (n = 4, 28.6%) and pediatric heme-oncology (n = 3, 21.4%). Clinical presentation commonly included vascular malformations (n = 8, 57.1%). Most pts were diagnosed with CLOVES (n = 12, 85.7%). Seven pts (50.0%) had documented lesions at dx, median of 2 (range, 1-13) lesions per pt, increasing after dx to 3 (range, 1-14). All pts reported PROS-related complications; 50.0% (n = 7) required hospitalization/ER visit. Musculoskeletal, neurological, and gastrointestinal related complications were each reported by ≥50% of pts. All pts required ≥1 surgery; ≥50% of pts had diagnostic, debulking, vascular, or other procedures. Median number of surgeries per pt was 7 (range, 1-28), corresponding to a median of 0.76 surgeries per pt per year. Eight pts (57.1%) received PROS related medications: 6 (42.9%) received alpelisib, 5 (35.7%) received sirolimus. Conclusions: While each pt is unique, similarities in the path to dx (eg, specialties involved) and disease history (eg, clinical presentation, symptoms experienced) exist. RWE abstracted from medical records rapidly provides data in an otherwise limited field, helping to address key questions. Preliminary results highlight the burden of PROS and the reliance on repetitive surgical interventions for management, suggesting there remains a high unmet medical need for effective therapeutic strategies.

Funding Acknowledgements Type of funding sources: None. BACKGROUND Exercise stress echocardiography (ESE) is a commonly used investigation for risk stratification in coronary artery disease (CAD). The added value of resting indices such as Global Longitudinal Strain (GLS) and Mechanical Dispersion (MD) to detect obstructive CAD is not well established and would be of significant clinical benefit. PURPOSE To evaluate the diagnostic value of GLS and MD at rest and post-exercise during ESE to detect obstructive CAD, defined by angiographic stenosis >70% in any major coronary artery. METHODS Retrospective cohort study of 80 consecutive patients who underwent ESE and had coronary angiography (invasive or CT) within 6 months. Retrospective speckle tracking strain analysis was performed on digitally archived video-loops, using vendor independent software. Data on demographics, medications, outcomes and ESE characteristics were collected and analysed. RESULTS In 49 (61.3%) patients with any CAD >70%, GLS at rest was lower (-13.9% ± 4.2 vs -16.1% ± 5.2, p-value = 0.04), and MD at rest was higher (81ms ± 43 vs 58ms ± 28, p-value = 0.008), when compared to patients without CAD >70%. GLS and MD measured post-exercise were not significantly different between groups. Ejection fraction (EF) and Wall Motion Score Index (WMSI) at rest and post-exercise were not significantly different between groups. A resting GLS cutpoint of -14% had a sensitivity and specificity of 57/68%, comparable to the development of new regional wall motion abnormalities (71/39%) and peak WMSI >1.2 (59/48%). Additionally, in 39 (48.8%) patients who had >70% stenosis in the left anterior descending (LAD) artery, LS in the LAD territory segments was lower (-16.2% ± 4.4 vs -18.3% ± 4.7, p-value = 0.04), when compared to patients without >70% stenosis in the LAD artery. CONCLUSION Resting GLS was lower and MD higher in patients undergoing ESE, who have any CAD >70% compared to patients who do not have any CAD >70%. Resting GLS and MD may increase diagnostic accuracy during ESE to predict obstructive CAD. Further prospective studies evaluating the utility of resting indices to predict functionally significant CAD are required.

Introduction: Myocardial infarction with non-obstructive coronary arteries (MINOCA) occurs in ~10% of all patients with acute myocardial infarction (AMI), with an over-representation amongst women. Remarkably, it is estimated that as many as 1 in 4 patients with MINOCA experience ongoing angina at 12 months despite having no flow-restricting stenoses in their epicardial arteries. This manuscript presents the rationale behind Randomized Evaluation of Beta Blocker and Angiotensin-converting enzyme inhibitors/Angiotensin Receptor Blocker Treatment (ACEI/ARB) for Post Infarct Angina in MINOCA patients—The MINOCA BAT post infarct angina sub study.Methods: This trial is a registry-based, randomized, parallel, open-label, multicenter trial with 2 × 2 factorial design. The primary aim is to determine whether oral beta blockade compared with no oral beta blockade, and ACEI/ARB compared with no ACEI/ARB, reduce post infarct angina in patients discharged after MINOCA without clinical signs of heart failure and with left ventricular ejection fraction ≥40%. A total of 664 patients will be randomized into four groups; (i) ACEI/ARB with beta blocker, (ii) beta blocker only, (iii) ACEI/ARB only, or (iv) neither ACEI/ARB nor beta blocker and followed for 12 months.Results: The trial is currently recruiting in Australia and Sweden. Fifty six patients have been recruited thus far. Both sexes were equally distributed (52% women and 48% men) and the mean age was 56.3 ± 9.9 years.Conclusions: It remains unclear whether conventional secondary preventive therapies are beneficial to MINOCA patients in regard to post infarct angina. Existing registry-based literature suggest cardioprotective agents are less likely to be used in MINOCA patients. Thus, results from this trial will provide insights for future treatment strategies and guidelines specific to MINOCA patients.

Introduction: Igneous compositions found in float rock within Gale crater have revealed previously unseen compositional diversity, with a range of chemistry that predominantly falls into basaltic and trachy-basaltic classification [1]. In addition, Gale sedimentary rocks, both float and in situ, record a combination of source compositions and diagenetic overprints [2,3]. We examine several float samples identified by the Mars Science Laboratory mission’s Curiosity rover at different sites: 1 target from the approach traverse to the Kimberley site (sol 544); 4 targets from Ireson Hill (circa. sol 1600); 1 target from the Bressay site (sol 2018), to investigate their origin and relationship to previous units as well as wider Martian igneous chemistry. We use data from the ChemCam LIBS, APXS, Mastcam (MCAM), Mars Hand Lens Imager (MAHLI) and ChemCam Remote Micro-Imager (RMI) cameras. These targets were selected on the basis of distinctive chemical compositions and textures, falling outside typical igneous Gale float classification [2]. We employ the MELTS software package [4] to investigate possible magmatic sources and evolution pathways for these samples. Float Rock Textures: Among the Ireson Hill samples, Pogy shows an unusual texture with two visually distinct phases (Fig. 1). A lighter toned phase makes up ~50% of Pogy’s texture, and the darker toned phase ~10% (measured through pixel counting of manually selected areas), with the remainder being interstitial material without distinct grains. Both phases are anhedral, with grain sizes typically ranging from 1-1.5 mm. The texture appears largely crystalline. It appears notably dissimilar in appearance to the local Stimson in situ and float rocks [5] found at Ireson Hill. Among the other Ireson Hill targets, Passagassawakeag is an instance of a well-defined Dreikanter, which hints at a harder, crystalline mineralogy (Fig. 2). The remaining targets, Quimby and Wassataquoik do not show such strong evidence for igneous origin in available RMI and Mastcam imagery, but also do not feature the sedimentary texture of surrounding bedrock and float targets, and we therefore include them as possible igneous targets in this analysis. The two remaining targets discussed here, Bindi and Askival, display similar textures to each other. Both rocks display cumulate texture (Fig. 3), with light-toned, subhedral mineral grains with sizes up to >10 mm accounting for the majority (65%-70% in Askival) of the texture and dark toned assemblages (30%-35% in Askival) poikilitically enclosing the light toned grains, as interstitial material. Examples of small dark crystals enclosed within the lighter phase are also present. Askival also displays limited (approx. 1.2%) light toned sulphate emplaced as interstitial material. When combined with chemical analysis (below) of the light-toned grains this identifies these samples as feldspathic cumulates. Compositions: Results for Pogy are presented SO3-free with a corresponding amount of CaO removed in order to account for excess CaSO4 present on Martian rock surfaces. Results were then recalculated to 100% total weight. Pogy’s APXS geochemical composition (Fig. 4) shows similarity in SiO2, Na2O, K2O, CaO, Al2O3 & TiO2 to the Adirondack-class basalt compositions predominant at the Gusev crater MER mission site, although it has a lower Mg#. However, we note that this similarity does not in itself establish an igneous origin for Pogy as Martian sedimentary rocks can also record igneous source compositions [1,3,5,7]. MELTS [4] modelling (Fig. 4) indicates that Pogy-like compositions can be generated by fractionation of magmatic compositions previously derived as parental to Adirondack-class basalts [9], with approximately 13% of the original mass removed through olivine fractionation. The exact conditions of magmatic evolution differ somewhat from the Gusev basalt pathways in order to account for the lower Mg# of Pogy’s composition compared to the Adirondack composition. Bindi and Askival display clearly feldspathic compositions for a subset of the ChemCam LIBS spots, where the targeted spot was on a light-toned grain. Dark toned grains have mafic compositions. The two targets overall chemistry is differentiated by a higher SiO2 abundance in Askival. Comparing other elemental oxide abundances to SiO2 (Fig. 5 reveals a trend away from the Bindi compositional area, which we interpret as evidence of post-cumulate formation silicification. Comparison of the Albite-Anorthite phase ratio (Fig. 6) between Askival and Bindi shows an overlap, indicating that the cumulates may have formed under similar conditions. We again use MELTS with a variety of input compositions. Modelling performed with the “Johnnie” (basaltic Gale crater target) composition (Fig. 6) produces feldspars with similar phase compositions to those seen in Askival and Bindi. Conclusions: Ireson Hill float rocks show a variety of textures and compositions, some of which e.g. Passagassawakeag and Pogy appear to be more crystalline than local Stimson bedrock and derived float. Pogy appers to be an igneous, plutonic rock, with an uncertain emplacement process at Ireson Hill. Comparing to known Gale compositions and rocks, suggests that the Pogy composition represents low pressure, low H2O, fractionation in a shallow crustal setting. This has been preserved either directly as an igneous rock or as a dominant source component in some Gale sedimentary units [5]. The Askival and Bindi float targets are feldspathic cumulates, with Askival’s composition showing evidence for alteration of an original state similar to Bindi. MELTS modelling indicates that these cumulates could have been derived from a source with similar composition to typical Gale crater basalts. References: [1] Edwards, P.H., et al.,. MAPS, 2017. 52(11): p.2931-2410. [2] Cousin, A., et al. Icarus, 2017. 288: p.265-283. 113622 [3] Bedford, C.C., et al.,. GCA, 2019. 246: p.234-266. [4] Ghiorso, M.S. et al. Eos, Trans AGU, 1994. 75(49): p.571-576. [5] Bedford, C.C., et al., Icarus, 2020. 341 [6] Yen et al., EPSL, 2017, 471: p.186-198 [7] Siebach, K.L., et al., Journal of Geophysical Research: Planets, 2017. 122(2): p.295-328. [8] McSween, H.Y., et al.. Science, 2004. 305: p.842-845. [9] Filiberto, J. and R. Dasgupta, EPSL, 2011. 304(3): p.527-537.

Myocardial perfusion scanning (MPS) is commonly used to assess patients with an intermediate to high risk of coronary artery disease. Concerns have been raised about the accuracy of this test. There is little recent data regarding the specificity of the MPS in the context of current medical therapy. The primary objective of this study is to determine the specificity of MPS in diagnosing obstructive coronary artery disease. A total of 184 patients fulfilled study criteria. The overall specificity of MPS for obstructive coronary artery disease was 54%.The only demographic variable that influenced specificity was gender: males with a specificity of 66% and females with a specificity of 29% (p-value = 0.001). These results suggest that the real world specificity of MPS is lower than previously indicated, particularly in the female population. The limitations proposed by the Cardiac Services Committee Report are therefore unlikely to improve patient outcomes.

Highly ordered thiol-ethylene bridged Periodic Mesoporous Organosilicas were synthesized directly from a homemade thiol-functionalized bis-silane precursor. These high surface area materials contain up to 4.3 mmol/g sulfur functions in the walls and can adsorb up to 1183 mg/g mercury ions. Raman spectroscopy reveals the existence of thiol and disulfide moieties. These groups have been evaluated by a combination of Raman spectroscopy, Ellman’s reagent and elemental analysis. The adsorption of mercury ions was evidenced by different techniques, including Raman, XPS and porosimetry, which indicate that thiol groups are highly accessible to mercury. Scanning transmission electron microscopy combined with EDX showed an even homogenous distribution of the sulfur atoms throughout the structure, and have revealed for the first time that a fraction of the adsorbed mercury is forming thiolate nanocrystals in the pores. The adsorbent is highly selective for mercury and can be regenerated and reused multiple times, maintaining its structure and functionalities and showing only a marginal loss of adsorption capacity after several runs.

The use of treadmill stress echocardiography (SE) for the diagnosis of nascent pulmonary hypertension (PH) has been hampered by a lack of well-defined, post-exercise pulmonary artery systolic pressure (PASP) values across representative age groups in a normal cohort.Five hundred and eleven subjects (mean age: 53 ±14, 68% female) with normal resting PASP were included in the study. All participants performed treadmill exercise using the Bruce protocol to a high level of perceived exertion. PASP was calculated before and immediately after exercise using Doppler assessment of tricuspid regurgitation. For the cohort, post-exercise PASP was 39 ± 7 mmHg (range: 23-64 mmHg) representing an increase of 11 ± 6 mmHg (44%) from resting values (P 0.001). The 95th centile values for post-exercise PASP were calculated for the following age cohorts: 30 years; 46 mmHg, 31-50 years; 50 mmHg, 51-70 years; 52 mmHg, 70 years; 53 mmHg. There was a modest independent correlation between post-exercise PASP and (i) increasing age and (ii) resting PASP (r2 = 0.35 and 0.49, respectively, P = 0.01).An increase of post-exercise PASP was seen in all patients undergoing SE in this study. Age was directly correlated with post-exercise PASP. Using normative data from healthy controls, treadmill SE-derived post-exercise PASP may be a useful adjunct in the diagnosis of PH.

Recent advances in cyber-infrastructure have enabled digital data sharing and ubiquitous network connectivity between scientific instruments and cloud-based storage infrastructure for uploading, storing, curating, and correlating of large amounts of materials and semiconductor fabrication data and metadata. However, there is still a significant number of scientific instruments running on old operating systems that are taken offline and cannot connect to the cloud infrastructure, due to security and network performance concerns. In this paper, we propose BRACELET - an edge-cloud infrastructure that augments the existing cloud-based infrastructure with edge devices and helps to tackle the unique performance & security challenges that scientific instruments face when they are connected to the cloud through public network. With BRACELET, we put a networked edge device, called cloudlet, in between the scientific instruments and the cloud as the middle tier of a three-tier hierarchy. The cloudlet will shape and protect the data traffic from scientific instruments to the cloud, and will play a foundational role in keeping the instruments connected throughout its lifetime, and continuously providing the otherwise missing performance and security features for the instrument as its operating system ages.

The fundamental plasticity mechanisms in thin freestanding Zr65Ni35 metallic glass films are investigated in order to unravel the origin of an outstanding strength/ductility balance. The deformation process is homogenous until fracture with no evidence of catastrophic shear banding. The creep/relaxation behaviour of the films was characterized by on-chip tensile testing, revealing an activation volume in the range 100–200 Å3. Advanced high-resolution transmission electron microscopy imaging and spectroscopy exhibit a very fine glassy nanostructure with well-defined dense Ni-rich clusters embedded in Zr-rich clusters of lower atomic density and a ~2–3 nm characteristic length scale. Nanobeam electron diffraction analysis reveals that the accumulation of plastic deformation at room-temperature correlates with monotonously increasing disruption of the local atomic order. These results provide experimental evidences of the dynamics of shear transformation zones activation in metallic glasses. The impact of the nanoscale structural heterogeneities on the mechanical properties including the rate dependent behaviour is discussed, shedding new light on the governing plasticity mechanisms in metallic glasses with initially heterogeneous atomic arrangement.

Utilization of Au and nanocrystalline diamond (NCD) as interlayers noticeably modifies the microstructure and field electron emission (FEE) properties of hexagonal boron nitride nanowalls (hBNNWs) grown on Si substrates. The FEE properties of hBNNWs on Au could be turned on at a low turn-on field of 14.3 V μm−1, attaining FEE current density of 2.58 mA cm−2 and life-time stability of 105 min. Transmission electron microscopy reveals that the Au-interlayer nucleates the hBN directly, preventing the formation of amorphous boron nitride (aBN) in the interface, resulting in enhanced FEE properties. But Au forms as droplets on the Si substrate forming again aBN at the interface. Conversely, hBNNWs on NCD shows superior in life-time stability of 287 min although it possesses inferior FEE properties in terms of larger turn-on field and lower FEE current density as compared to that of hBNNWs-Au. The uniform and continuous NCD film on Si also circumvents the formation of aBN phases and allows hBN to grow directly on NCD. Incorporation of carbon in hBNNWs from the NCD-interlayer improves the conductivity of hBNNWs, which assists in transporting the electrons efficiently from NCD to hBNNWs that results in better field emission of electrons with high life-time stability.

Evolution of crystalline phases with temperature has been studied in materials produced by high-pressure high-temperature treatment of 9-borabicyclo[3.3.1]nonane dimer (9BBN), triphenylborane and trimesitylborane. The boron-doped diamond nanoparticles with a size below 10 nm were obtained at 8–9 GPa and temperatures 970–1250 °C from 9BBN only. Bridged structure and the presence of boron atom in the carbon cycle of 9BBN were revealed to be a key point for the direct synthesis of doped diamond nanocrystals. The diffusional transformation of the disordered carbon phase is suggested to be the main mechanism of the nanodiamond formation from 9BBN in the temperature range of 970–1400 °C. Aqueous suspensions of primary boron-doped diamond nanocrystals were prepared upon removal of non-diamond phases that opens wide opportunities for application of this new nanomaterial in electronics and biotechnologies.

Diamond is a promising material for a number of bio-applications, including the fabrication of platforms for attachment and investigation of neurons and of neuroprostheses, such as retinal implants. In the current work ultrananocrystalline diamond (UNCD) films were deposited by microwave plasma chemical vapor deposition, modified by UV/O-3 treatment or NH3 plasma, and comprehensively characterized with respect to their bulk and surface properties, such as crystallinity, topography, composition and chemical bonding nature. The interactions of insect circadian pacemaker neurons with UNCD surfaces with H-, O- and NH2-terminations were investigated with respect to cell density and viability. The fast and strong attachment achieved without application of adhesion proteins allowed for advantageous modification of dispersion protocols for the preparation of primary cell cultures. Centrifugation steps, which are employed for pelletizing dispersed cells to separate them from dispersing enzymes, easily damage neurons. Now centrifugation can be avoided since dispersed neurons quickly and strongly attach to the UNCD surfaces. Enzyme solutions can be easily washed off without losing many of the dispersed cells. No adverse effects on the cell viability and physiological responses were observed as revealed by calcium imaging. Furthermore, the enhanced attachment of the neurons, especially on the modified UNCD surfaces, was especially advantageous for the immunocytochemical procedures with the cell cultures. The cell losses during washing steps were significantly reduced by one order of magnitude in comparison to controls. In addition, the integration of a titanium grid structure under the UNCD films allowed for individual assignment of physiologically characterized neurons to immunocytochemically stained cells. Thus, employing UNCD surfaces free of foreign proteins improves cell culture protocols and immunocytochemistry with cultured cells. The fast and strong attachment of neurons was attributed to a favorable combination of topography, surface chemistry and wettability. (C) 2016 Elsevier B.V. All rights reserved.

Hexagonal boron nitride nanowall thin films were deposited on Si(100) substrates using a Ar(51%)/N-2(44%)/H-2(5%) gas mixture by unbalanced radio frequency sputtering. The effects of various target-to-substrate distances, substrate temperatures, and substrate tilting angles were investigated. When the substrate is close to the target, hydrogen etching plays a significant role in the film growth, while the effect is negligible for films deposited at a farther distance. The relative quantity of defects was measured by a non-destructive infrared spectroscopy technique that characterized the hydrogen incorporation at dangling nitrogen bonds at defect sites in the deposited films. Despite the films deposited at different substrate tilting angles, the nanowalls of those films were found to consistently grow vertical to the substrate surface, independent of the tilting angle. This implies that chemical processes, rather than physical ones, govern the growth of the nanowalls. The results also reveal that the degree of nanowall crystallization is tunable by varying the growth parameters. Finally, evidence of hydrogen desorption during vacuum annealing is given based on measurements of infrared stretching (E-1u) and bending (A(2u)) modes of the optical phonons, and the H-N vibration mode.

Antiferromagnetic(AFM)|ferrimagnetic(FiM) core|shell (CS) nanoparticles (NPs) of formula Co0.3Fe0.7O|Co0.6Fe2.4O4 with mean diameter from 6 to 18 nm have been synthesized through a one-pot thermal decomposition process. The CS structure has been generated by topotaxial oxidation of the core region, leading to the formation of a highly monodisperse single inverted AFM|FiM CS system with variable AFM-core diameter and constant FiM-shell thickness (∼2 nm). The sharp interface, the high structural matching between both phases, and the good crystallinity of the AFM material have been structurally demonstrated and are corroborated by the robust exchange-coupling between AFM and FiM phases, which gives rise to one among the largest exchange bias (HE) values ever reported for CS NPs (8.6 kOe) and to a strongly enhanced coercive field (HC). In addition, the investigation of the magnetic properties as a function of the AFM-core size (dAFM), revealed a nonmonotonous trend of both HC and HE, which display a maximum value for dAFM = 5 nm (19.3 and 8.6 kOe, respectively). These properties induce a huge improvement of the capability of storing energy of the material, a result which suggests that the combination of highly anisotropic AFM|FiM materials can be an efficient strategy toward the realization of novel rare-earth-free permanent magnets.

This work presents a morphological and structural analysis of CVD diamond growth on silicon from nanodiamond seeds covered by a 50 nm thick chromium layer. The role of carbon diffusion as well as chromium and carbon silicide formation is analyzed. The local diamond environment is investigated by scanning transmission electron microscopy in combination with electron energy-loss spectroscopy. The evolution of the diamond phase composition (sp(3)/sp(2)) is evaluated by micro-Raman spectroscopy. Raman and X-ray diffraction analysis are used to identify the interfacial phases formed during CVD growth. Based upon the observed morphological and structural evolution, a diamond growth model from nanodiamond seeds buried beneath a thin Cr layer is proposed. (C) 2016 Elsevier B.V. All rights reserved.

Simple methods for producing noble metal catalysts with well-defined active sites and improved performance are highly desired in the chemical industry. However, the development of such methods still presents a formidable synthetic challenge. Here, we demonstrate a one-pot synthesis route for the controlled production of bimetallic Pt-In catalysts based on the single-step formation of Mg,Al,Pt,In-containing layered double hydroxides (LDHs). Besides their simple synthesis, these Pt-In catalysts exhibit superior propane dehydrogenation activity compared to their multi-step synthesized analogs. The presented material serves as a showcase for the one-pot synthesis of a broader class of LDH-derived mono- and multimetallic Pt catalysts. The compositional flexibility provided by LDH materials can pave the way towards high-performing Pt-based catalysts with tunable physicochemical properties.

A thin film of heavily B-doped diamond has been grown epitaxially by microwave plasma chemical vapor deposition on an undoped diamond layer, on top of a Ir/YSZ/Si(001) substrate stack, to study the boron segregation and boron environment at the dislocations present in the film. The density and nature of the dislocations were investigated by conventional and weak-beam dark-field transmission electron microscopy techniques, revealing the presence of two types of dislocations: edge and mixed-type 45 degrees dislocations. The presence and distribution of B in the sample was studied using annular dark-field scanning transmission electron microscopy and spatially resolved electron energy-loss spectroscopy. Using these techniques, a segregation of B at the dislocations in the film is evidenced, which is shown to be intermittent along the dislocation. A single edge-type dislocation was selected to study the distribution of the boron surrounding the dislocation core. By imaging this defect at atomic resolution, the boron is revealed to segregate towards the tensile strain field surrounding the edge-type dislocations. An investigation of the fine structure of the B-K edge at the dislocation core shows that the boron is partially substitutionally incorporated into the diamond lattice and partially present in a lower coordination (sp(2)-like hybridization).

Hydrogen plays an essential role during the in situ assembly of tailored catalytic materials, and serves as key ingredient in multifarious chemical reactions promoted by these catalysts. Despite intensive debate for several decades, the existence and nature of hydrogen-involved mechanisms - such as hydrogen-spillover, surface migration - have not been unambiguously proven and elucidated up to date. Here, Pt-Ga alloy formation is used as a probe reaction to study the behavior and atomic transport of H and Ga, starting from Pt nanoparticles on hydrotalcite-derived Mg(Ga)(Al)O-x supports. In situ XANES spectroscopy, time-resolved TAP kinetic experiments, HAADF-STEM imaging and EDX mapping are combined to probe Pt, Ga and H in a series of H-2 reduction experiments up to 650 degrees C. Mg(Ga)(Al)O-x by itself dissociates hydrogen, but these dissociated hydrogen species do not induce significant reduction of Ga3+ cations in the support. Only in the presence of Pt, partial reduction of Ga3+ into Ga delta+ is observed, suggesting that different reaction mechanisms dominate for Pt- and Mg(Ga)(Al)O-x-dissociated hydrogen species. This partial reduction of Ga3+ is made possible by Pt-dissociated H species which spillover onto non-reducible Mg(Al)O-x or partially reducible Mg(Ga)(Al) Ox and undergo long-range transport over the support surface. Moderately mobile Ga delta+Ox migrates towards Pt clusters, where Ga delta+ is only fully reduced to Ga-0 on condition of immediate stabilization inside Pt-Ga alloyed nanoparticles.

Based on micro-Raman spectroscopy (μRS) and X-ray photoelectron spectroscopy (XPS), we study the structural damage incurred in monolayer (1L) and few-layer (FL) graphene subjected to atomic-layer deposition of HfO2 and Al2O3 upon different oxygen plasma power levels. We evaluate the damage level and the influence of the HfO2 thickness on graphene. The results indicate that in the case of Al2O3/graphene, whether 1L or FL graphene is strongly damaged under our process conditions. For the case of HfO2/graphene, μRS analysis clearly shows that FL graphene is less disordered than 1L graphene. In addition, the damage levels in FL graphene decrease with the number of layers. Moreover, the FL graphene damage is inversely proportional to the thickness of HfO2 film. Particularly, the bottom layer of twisted bilayer (t-2L) has the salient features of 1L graphene. Therefore, FL graphene allows for controlling/limiting the degree of defect during the PE-ALD HfO2 of dielectrics and could be a good starting material for building field effect transistors, sensors, touch screens and solar cells. Besides, the formation of Hf-C bonds may favor growing high-quality and uniform-coverage dielectric. HfO2 could be a suitable high-K gate dielectric with a scaling capability down to sub-5-nm for graphene-based transistors.

This chapter sets out to cover some of the pitfalls in applying “common sense” to legal decision making relating to the asylum process and the need to engage with the wider body of general psychological knowledge. We set out a brief summary of the law, and comment on the central issue of credibility. Because the asylum seeker rarely has objective documentation of their persecution, the decision-maker usually has to consider two primary issues – first if the claim meets the threshold for acceptance and second if the claim is to be believed (credibility). Memory is taken as an example of a process that may influence the asylum claim and/or decision; for example, discrepant reporting is often taken as proof of deceit. The scientific evidence in fact suggests that this is an erroneous assumption, that memory is not fixed. It is common for memory, even memory for traumatic events, to change. It is argued that there is a need to apply expert psychological knowledge, not just in the preparation of medico-legal reports on individuals but also in making the whole system of legal decision-making more psychologically informed and more consistent with the scientific literature. After a brief consideration of interviewing issues, there is also reference to both the potential impact of vicarious traumatisation on decision-makers and the difficulties in law of tolerating uncertainty.

The blocking of specific protein-protein interactions using nanoparticles is an emerging alternative to small molecule-based therapeutic interventions. However, the nanoparticles designed as "artificial proteins" generally require modification of their surface with (bio)organic molecules and/or polymers to ensure their selectivity and specificity of action. Here, we show that nanosized diamond crystals (nanodiamonds, NDs) without any synthetically installed (bio)organic interface enable the specific and efficient targeting of the family of extracellular signalling molecules known as fibroblast growth factors (FGFs). We found that low nanomolar solutions of detonation NDs with positive-potential strongly associate with multiple FGF ligands present at sub-nanomolar concentrations and effectively neutralize the effects of FGF signalling in cells without interfering with other growth factor systems and serum proteins unrelated to FGFs. We identified an evolutionarily conserved FGF recognition motif, 17 amino acids long, that contributes to the selectivity of the ND-FGF interaction. In addition, we inserted this motif into a de novo constructed chimeric protein, which significantly improved its interaction with NDs. We demonstrated that the interaction of NDs, as purely inorganic nanoparticles, with proteins can mitigate pathological FGF signalling and promote the restoration of cartilage growth in a mouse limb explant model. Based on our observations, we foresee that NDs may potentially be applied as nano therapeutics to neutralize disease-related activities of FGFs in vivo. (C) 2018 The Authors. Published by Elsevier Ltd.

Aims: We sought to evaluate the incidence of polypharmacy in patients referred for pulmonary hypertension assessment, assess the relationship of polypharmacy to the presence of co-morbidity and document the influence of polypharmacy and co-morbidity on unplanned readmissions and mortality in this cohort.Methods: We performed an audit of outpatient clinical medical records for 215 consecutive patients referred to a tertiary referral centre for pulmonary hypertension assessment between March 2009 and April 2016. Data on number and class of medications were recorded, as well as past medical history and investigations relevant to assessment of pulmonary hypertension.Results: At the time of pulmonary hypertension evaluation, patients were prescribed a mean of 8 ± 4 medications with 83.2% of patients being on 5 or more regularly prescribed medications. Taking 8 or more medications was associated with co-morbidity, as assessed by the Charlson Co-morbidity Index, and reduced exercise capacity. The presence of co-morbidity resulted in a significantly higher risk of unplanned admission. The presence of polypharmacy is a marker of important co-morbidity, identifying a group at high risk.Conclusion: Patients referred for assessment of pulmonary hypertension had high rates of polypharmacy reflecting extensive comorbidity, which in turn predicts adverse outcome in this patient population. The presence of polypharmacy should be considered a simple clinical marker of co-morbidity, increased risk and adverse outcome.

The covalent triazine framework, CTF-1, served as host material for the in situ synthesis of Fe

Polycrystalline boron-doped superconducting diamond, synthesized at high pressure and high temperature (HPHT) via a reaction of a single piece of crystalline boron with monolithic graphite, has been investigated by analytical transmission electron microscopy. The local boron distribution and boron environment have been studied by a combination of (scanning) transmission electron microscopy ((S)TEM) and spatially resolved electron energy-loss spectroscopy (EELS). High resolution TEM imaging and EELS elemental mapping have established, for the first time, the presence of largely crystalline diamond-diamond grain boundaries within the material and have evidenced the presence of substitutional boron dopants within individual diamond grains. Confirmation of the presence of substitutional B dopants has been obtained through comparison of acquired boron K-edge EELS fine structures with known references. This confirmation is important to understand the origin of superconductivity in polycrystalline B-doped diamond. In addition to the substitutional boron doping, boron-rich inclusions and triple-points, both amorphous and crystalline, with chemical compositions close to boron carbide B4C, are evidenced. (C) 2015 Elsevier Ltd. All rights reserved.

In this article, we report on the synthesis of thin, epitaxial films of the transparent conductive oxide Al:ZnO on (0001)-oriented synthetic sapphire substrates by DC sputtering from targets with a nominal 1 at.% Al substitution. The deposition was carried out at an unusually low substrate temperature of only 250 °C in argon–oxygen mixtures as well as in pure argon. The impact of the process–gas composition on the morphology was analysed by transmission electron microscopy, revealing epitaxial growth in all the cases with a minor impact of the process parameters on the resulting grain sizes. The transport properties resistivity, Hall effect and magnetoresistance were studied in the range from 10 to 300 K in DC and pulsed magnetic fields up to 45 T. While the carrier density and mobility are widely temperature independent, we identified a low field–low temperature regime in which the magnetoresistance shows an anomalous, negative behaviour. At higher fields and temperatures, the magnetoresistance exhibits a more conventional, positive curvature with increasing field strength. As a possible explanation, we propose carrier scattering at localised magnetic trace impurities and magnetic correlations. Cross-sectional HAADF-STEM image of an Al:ZnO film grown without oxygen in the sputtering gas. The inset is a false-colour [100] high resolution STEM image (inverted annular bright field: green, annular dark-field: red) of the ZnO crystal structure.

The uniform dispersion of functional oxide nanoparticles inside ordered mesoporous silica to tailor optical, electronic, and magnetic properties for biomedical and environmental applications is a scientific challenge. Herein, we demonstrate for the very first time the morphological effect of platelet-driven confined growth of hematite iron oxide (alpha-Fe2O3) nanorods inside the mesochannels of ordered mesoporous silica COK-12 material denoted as alpha-Fe2O3@COK-12. The inclusion of the alpha-Fe2O3 nanorods in COK-12 particles is studied in detail using high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-ray (EDX) spectroscopy and electron tomography. High resolution imaging and EDX spectroscopy provide information about the particle size, shape and crystal phase of the loaded alpha-Fe2O3 material, while electron tomography provides detailed information on the spreading of the nanorods throughout the COK-12 host in three-dimension. This nanocomposite material, having a semiconductor band gap energy of 2.50 eV according to diffuse reflectance spectroscopy, demonstrates an improved visible light photocatalytic degradation activity with rhodamine 6G and 1-adamantanol model compounds.

This study is focused on thermoresponsive glycogen-graft-poly(2-alkyl-2-oxazolines), a new group of nanostructured hybrid dendrimeric stimuli-responsive polymers connecting the body's own biodegradable polysaccharidic dendrimer glycogen with the widely tuneable thermoresponsive behavior of polypeptide-analogic poly(2-alkyl-2-oxazolines), which are known to be biocompatible. Glycogen-graft-poly(2-alkyl-2-oxazolines) were prepared by a simple one-pot two-step procedure involving cationic ring-opening polymerization of 2-alkyl-2-oxazolines followed by termination of the living cationic ends with sodium glycogenate. As confirmed by light and X-ray scattering, as well as cryo-transmission electron microscopy, the grafted dendrimer structure allows easy adjustment of the cloud point temperature, the concentration dependence and nanostructure of the self-assembled phase separated polymer by crosstalk during graft composition, the graft length and the grafting density, in a very wide range.

[EN] The realization of metal nanoparticles (NPs) with bimetallic character and distinct composition for specific catalytic applications is an intensively studied field. Due to the synergy between metals, most bimetallic particles exhibit unique properties that are hardly provided by the individual monometallic counterparts. However, as small-sized NPs possess high surface energy, agglomeration during catalytic reactions is favored. Sufficient stabilization can be achieved by confinement of NPs in porous support materials. In this sense, metal organic frameworks (MOFs) in particular have gained a lot of attention during the last years; however, encapsulation of bimetallic species remains challenging. Herein, the exclusive embedding of preformed core shell PdPt and RuPt NPs into chemically robust Zr-based MOFs is presented. Microstructural characterization manifests partial retention of the core shell systems after successful encapsulation without harming the crystallinity of the microporous support. The resulting chemically robust NP@UiO-66 materials exhibit enhanced catalytic activity towards the liquid-phase hydrogenation of nitrobenzene, competitive with commercially used Pt on activated carbon, but with superior size-selectivity for sterically varied substrates., This work is supported by the Cluster of Excellence RESOLV (EXC 1069) funded by the Deutsche Forschungsgemeinschaft (DFG).

The coupling of light absorbers to cocatalysts with well-designed optical and catalytic properties is of fundamental importance for the development of efficient photoelectrocatalytic devices for solar-driven water splitting. We achieved an effective loading of visible-light-active porous hybrid photoanodes for water photooxidation with ultrasmall (similar to 1-2 nm), highly disordered CoO(OH)(x) nanoparticles using a two-step impregnation method. Under visible light (lambda > 420 nm) irradiation, the resulting photoanodes significantly outperformed photoanodes loaded with conventional cobalt-based cocatalyst (Co-Pi) comprising larger nanoparticles (similar to 5 nm) in terms of both Faradaic efficiency of oxygen evolution (by the factor of 2) and performance stability under long-term irradiation. A combination of STEM, XAS, cyclic voltammetry, and photoelectrochemical techniques was used to elucidate the advantages of using ultrasmall CoO(OH)(x) nanoparticles as cocatalysts. Specifically, due to the high transparency of ultrasmall CoO(OH)(x) nanoparticles in the visible range, higher loading of porous photoanodes with cobalt catalytic sites can be achieved, while the photocurrent losses due to parasitic light absorption by the cocatalyst are minimized. Notably, a significant enhancement in stability of ultrasmall CoO(OH)(x) nanoparticles in borate electrolytes as compared to phosphate electrolytes has been observed. EXAFS data recorded before and after photoelectrocatalysis indicated that the effect of the electrolyte on the stability can be explained by the difference in structural ordering dictated by different interaction of the electrolyte anions with cobalt ions, as corroborated by DFT calculations. This study highlights the strong impact of structural and optical properties of cocatalysts as well as the strong influence of the electrolyte composition on the activity and stability of photoelectrocatalytic systems comprising transition metal oxide electrocatalysts.

This chapter focuses on recent advances in the characterization of detonation nanodiamond material by aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy. The interpretation of the spectroscopic data is assisted by density functional theory calculations. Several practical examples, including pristine nanodiamond, surface modified and coated nanodiamond, as well as boron and nitrogen doped diamond material are presented to easily understand the capabilities of the techniques.