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In the present study, the creep deformation mechanisms of a eutectic Mo–Si–Ti alloy (comprising a body‐centered solid solution and a hexagonal silicide) are verified. The microstructural changes occurring at the various microstructural length scales are correlated to the nature of the creep curve. The creep curve exhibits a transient strain‐hardening region followed by a distinct minimum and then creep rate accelerates after that. The formation of a high fraction of disperse (Ti,Mo)5Si3 precipitates in the solid solution lead to significant strengthening in the transient creep regime. By the simultaneous decrease of the initially high dislocation density in the solid solution, diffusional creep contributes to effective creep behavior. At the minimum, the load and strain are also carried by the silicide phase which undergoes plastic deformation. Continuous coarsening of precipitates and loss of precipitation strengthening in the solid solution and dynamic recovery in the silicide phase lead to creep acceleration. [ABSTRACT FROM AUTHOR]

Herein, the development of directional solidification for a novel high‐temperature Mo–20Si–52.8Ti (at%) ternary alloy using a modified Bridgeman type apparatus is presented. The resulting alloy exhibits a microstructure consisting of a body‐centered cubic solid solution (BCCss) and a hexagonal silicide (Ti,Mo)5Si3 with approximate volume fractions of 50% for each phase. The phases exhibit a crystallographic orientation relationship with (123)BCCSS||(0001)(Ti,Mo)5Si3$\left(\left(\right. 123 \left.\right)\right)_{\left(\text{BCC}\right)_{\text{SS}}} \left|\right. \left|\right. \left(\left(\right. 0001 \left.\right)\right)_{\left(\left(\right. \text{Ti} , \text{Mo} \left.\right)\right)_{5} \left(\text{Si}\right)_{3}}$ and [111¯]BCCSS||[112¯0](Ti,Mo)5Si3$\left(\left[\right. 11 \bar{1} \left]\right.\right)_{\left(\text{BCC}\right)_{\text{SS}}} \left|\right. \left|\right. \left(\left[\right. 11 \bar{2} 0 \left]\right.\right)_{\left(\left(\right. \text{Ti} , \text{Mo} \left.\right)\right)_{5} \left(\text{Si}\right)_{3}}$. Different solidification velocities are imposed, which reveal an inverse relationship to the lamellar spacing according to a Jackson–Hunt type scaling. Mechanical characterization using Vickers indentation demonstrates that the BCCss accommodates plasticity through dislocation motion, while the silicide phase exhibits high hardness and brittleness, serving as a crack initiation site. Crack propagation is arrested and deflected at the interface to the BCCss. Fracture toughness measurements via indentation yield a fracture toughness of 3.7 MPa√m for the silicide, somewhat higher than previously reported values for Nb‐, Mo‐, and Cr‐based silicides at room temperature. The directionally solidified specimens show an enhanced fracture toughness attributed to a greater BCCss length scale; thus, combining the ductile and hard phases results in a ductile‐phase toughened intermetallic composite. The findings open up new possibilities for the design of advanced intermetallic composites with improved toughness performance. [ABSTRACT FROM AUTHOR]

Body‐centered‐cubic refractory high‐entropy alloys are promising for high‐temperature structural applications due to their exceptional properties, particularly in terms of yield strength at elevated temperatures. For certain alloy systems, such as Mo–Ti–Cr–Al, both disordered (A2) and ordered (B2) crystal structures are possible. In this particular system, a solid‐state transformation from A2 to B2 during cooling occurs. For Al concentrations above ≈10 at%, B2 order is obtained from the transformation temperature down to room temperature (RT), while A2 is stable above RT below the critical Al content. Herein, two alloys from the Mo–Ti–Cr–Al system close to the transition between A2 and B2 are investigated. Nanoindentation tests reveal that the magnitude of strain rate sensitivity for both alloys is small compared to classical alloys, however, significantly temperature dependent up to the strength plateau temperatures. The yield strength plateau, which is insensitive to the strain rate, is observed at temperatures exceeding 573 K. Modeling of solid solution strengthening reproduces the experimental data in the Al‐lean A2 alloys. However, the observed discontinuous increase of strength in the Al‐rich B2 alloys can only be rationalized by the appearance of B2 order and to no significant other obvious strengthening mechanisms. [ABSTRACT FROM AUTHOR]

The high‐affinity IgE receptor FcεRI is the mast cell (MC) receptor responsible for the involvement of MCs in IgE‐associated allergic disorders. Activation of the FcεRI is achieved via crosslinking by multivalent antigen (Ag) recognized by IgE resulting in degranulation and proinflammatory cytokine production. In comparison to the T‐ and B‐cell receptor complexes, for which several co‐receptors orchestrating the initial signaling events have been described, information is scarce about FcεRI‐associated proteins. Additionally, it is unclear how FcεRI signaling synergizes with input from other receptors and how regulators affect this synergistic response. We found that the HDL receptor SR‐BI (gene name: Scarb1/SCARB1) is expressed in MCs, functionally associates with FcεRI, and regulates the plasma membrane cholesterol content in cholesterol‐rich plasma membrane nanodomains. This impacted the activation of MCs upon co‐stimulation of the FcεRI with receptors known to synergize with FcεRI signaling. Amongst them, we investigated the co‐activation of the FcεRI with the receptor tyrosine kinase KIT, the IL‐33 receptor, and GPCRs activated by adenosine or PGE2. Scarb1‐deficient bone marrow‐derived MCs showed reduced cytokine secretion upon co‐stimulation conditions suggesting a role for plasma membrane‐associated cholesterol regulating respective MC activation. Mimicking Scarb1 deficiency by cholesterol depletion employing MβCD, we identified PKB and PLCγ1 as cholesterol‐sensitive proteins downstream of FcεRI activation in bone marrow‐derived MCs. When MCs were co‐stimulated with stem cell factor (SCF) and Ag, PLCγ1 activation was boosted, which could be mitigated by cholesterol depletion and SR‐BI inhibition. Similarly, SR‐BI inhibition attenuated the synergistic response to PGE2 and anti‐IgE in the human ROSAKIT WT MC line, suggesting that SR‐BI is a crucial regulator of synergistic MC activation. [ABSTRACT FROM AUTHOR]

Linear transportation infrastructures (LTIs) are established drivers of habitat fragmentation and barrier effects. Yet, they represent an increasing surface of managed seminatural habitats where increased consideration of biodiversity outputs is needed in an era of global biodiversity decline. A combined effort by both scientists and stakeholders is, therefore, needed to evaluate the promises and limits of these alternatives so that they best achieve their conservation potential. Our study explores the effects of forest powerline clearings on biodiversity, as well as the potential benefits of integrated vegetation management (IVM) as alternatives to clear‐cuts. We recorded the acoustic activity at 35 pairs of forest/clearing stations in two forested regions of France in 2021. Our results suggest that powerline clearings represent increased movement opportunities for bats and, most particularly, edge‐foraging species. They also provide suitable habitats for bush‐cricket species, particularly species requiring thermophilic conditions. We detected no direct benefit from IVM on bat communities. However, bush‐cricket communities appeared richer, more acoustically active, and statistically different from adjacent forests in clearings favoring secondary vegetation compared with clear‐cut ones. This collaborative study provides data on understudied taxa in the context of LTIs and sheds light on conservation promises and limits associated with their management. [ABSTRACT FROM AUTHOR]

A [2+3] chiral covalent organic cage is produced through a dynamic covalent chemistry approach by mixing two readily available building units, viz. an enantiopure 3,3'‐diformyl 2,2'‐BINOL compound (A) with a triamino spacer (B). The two enantiomeric (R,R,R) and (S,S,S) forms of the cage C are formed nearly quantitatively thanks to the reversibility of the imine linkage. The X‐ray diffraction analysis of cage (S,S,S)‐C highlights that the six OH functions of the BINOL fragments are positioned inside the cage cavity. Upon reduction of the imine bonds of cage C, the amine cage D is obtained. The ability of the cage D to host the 1‐phenylethylammonium cation (EH+) as a guest is evaluated through UV, CD and DOSY NMR studies. A higher binding constant for (R)‐EH+ cation (Ka=1.7 106±10 % M−1) related to (S)‐EH+ (Ka=0.9 106±10 % M−1) is determined in the presence of the (R,R,R)‐D cage. This enantiopreference is in close agreement with molecular dynamics simulation. [ABSTRACT FROM AUTHOR]

In this study, the simulation of a vacuum forming process employing a micromechanical inspired viscoelastic–viscoplastic model is investigated. In the vacuum forming process, a plastic sheet is heated above the glass transition temperature and subsequently forced into a mold by applying a vacuum. The model consists of a generalized Maxwell model combined with an dissipative element in series. Each Maxwell element incorporates a hyperelastic element in series with a viscous element based on a hyperbolical law. While the generalized Maxwell model considers the relaxation due to molecular alignment, the additional viscous element is a modification based on the approach of Bergström and thus considers molecular chain reptation. The model is designed with the aim to converge to the generalized linear Maxwell model in the limit of small deformation. Furthermore, the viscous modeling is temperature activated and follows the Williams–Landel–Ferry approach in the limit of linear viscoelasticity. To simulate rheological standard experiments, a physical‐network‐based implementation into Simscape is presented. To validate the performance of the model in thermoforming, it is implemented into Fortran programming language for finite element simulation with Abaqus/Explicit. It can be shown that the simulation is able to predict the thickness in high correlation with experimental results. [ABSTRACT FROM AUTHOR]

Enhancing electronic transport properties of thermoelectric oxides is of great technological importance. Oxides are promising candidates for waste heat harvesting at elevated temperatures as well as for electricity generation in low‐power applications. To this purpose, fundamental understanding of their electrical and thermal conduction mechanisms is essential. Herein, the conduction mechanism of CaMnO3 materials is focused on and how dopant identity and amount alter the kinetic properties of charge transport is investigated. Ca1−xRxMnO3 compounds with R = Y and La are synthesized, where 0 ≤ x ≤ 0.13, and the electrical conductivity and Seebeck coefficient for temperatures ranging from 300 to 1050 K, indicating that Y‐doped compounds are usually more conductive than their La‐doped counterparts, are measured. Analysis of both in terms of the small polaron hopping model reveals that Y doping reduces conduction activation energies, resulting in higher electrical conductivity and charge carrier mobility. Remarkably high values of thermoelectric power factor for the Ca0.97La0.03MnO3 compound, for example, 300 μWm−1 K−2 at 1050 K are observed; furthermore, these values are preserved for a wide temperature range, rendering this compound a good candidate for heat‐to‐electrical power generation at elevated temperatures. [ABSTRACT FROM AUTHOR]

Genes carrying high‐penetrance germline mutations may also be associated with cancer susceptibility through common low‐penetrance genetic variants. To increase the knowledge on genetic pancreatic ductal adenocarcinoma (PDAC) aetiology, the common genetic variability of PDAC familial genes was analysed in our study. We conducted a multiphase study analysing 7745 single nucleotide polymorphisms (SNPs) from 29 genes reported to harbour a high‐penetrance PDAC‐associated mutation in at least one published study. To assess the effect of the SNPs on PDAC risk, a total of 14 666 PDAC cases and 221 897 controls across five different studies were analysed. The T allele of the rs1412832 polymorphism, that is situated in the CDKN2B‐AS1/ANRIL, showed a genome‐wide significant association with increased risk of developing PDAC (OR = 1.11, 95% CI = 1.07‐1.15, P = 5.25 × 10−9). CDKN2B‐AS1/ANRIL is a long noncoding RNA, situated in 9p21.3, and regulates many target genes, among which CDKN2A (p16) that frequently shows deleterious somatic and germline mutations and deregulation in PDAC. Our results strongly support the role of the genetic variability of the 9p21.3 region in PDAC aetiopathogenesis and highlight the importance of secondary analysis as a tool for discovering new risk loci in complex human diseases. [ABSTRACT FROM AUTHOR]

Parts for metallurgical applications made from refractory metal–ceramic composites offer improved thermal shock resistance due to their capability for resistive heating compared to ones made solely from ceramics such as Al2O3. The combination of Al2O3 and Nb is intriguing as both show similar thermal expansion behavior over a wide temperature range. The high affinity of Nb for O to form nonprotective oxides, however, hampers its use in oxidative environments. Formation of such phases at the ceramic–metal interface can have detrimental effects on the cohesion of the composites. For this work, nanocrystalline Nb films are deposited on sapphire substrates by magnetron sputtering to study diffusion of O and high‐temperature phase formation at a refractory metal–ceramic interface during heat treatment under Ar at 1600 °C. A combined approach of atom probe tomography and transmission electron microscopy for compositional and crystallographic analyses reveals that at triple junctions of the sapphire–Nb interface with Nb grain boundaries, heterogeneous nucleation of nanoscale NbO2 occurs, which further reacts with Al2O3 to form AlNbO4, while the Nb film itself remains metallic. Fast O transport through grain boundaries leads to internal oxidation at the interface, whereas regions further away from Nb grain boundaries remain unchanged. [ABSTRACT FROM AUTHOR]

Oligomers designed to form a helix‐turn‐helix super‐secondary structure have been prepared by covalently bridging aliphatic oligourea foldamer helices with either rigid aromatic or more flexible aliphatic spacers. The relative helix orientation in these dimers was investigated at high resolution using X‐ray diffraction analysis. In several cases, racemic crystallography was used to facilitate crystallization and structure determination. All structures were solved by direct methods. Well‐defined parallel helical hairpin motifs were observed in all cases when 4,4′‐methylene diphenyl diisocyanate was employed as a dimerizing agent, irrespective of primary sequence and chain length. [ABSTRACT FROM AUTHOR]

Aim: To evaluate the efficacy of coronally advanced flap (CAF) versus tunnel technique (TUN) in covering isolated mid‐facial peri‐implant soft tissue dehiscences (PSTDs). Materials and Methods: Twenty‐eight participants presenting with isolated non‐molar implants exhibiting PSTDs were enrolled and randomized to receive either CAF or TUN, both with a connective tissue graft (CTG). The primary outcome of the study was the percentage of mean PSTD coverage at 12 months. Secondary endpoints included the frequency of complete PSTD coverage, changes in keratinized mucosa width (KMW) and horizontal mucosal thickness (MT), as assessed with transgingival probing, 3D optical scanning and ultrasonography, professional aesthetic evaluation and patient‐reported outcome measures (PROMs). Results: At 12 months, the mean PSTD coverage of the CAF and TUN groups was 90.23% and 59.76%, respectively (p =.03). CAF‐treated sites showed a substantially higher frequency of complete PSTD coverage (p =.07), together with significantly greater gain of KMW (p =.01), increase in MT (p =.02), volumetric gain (p <.01) and professional aesthetic outcomes (p =.01). Both interventions showed an improvement in patient‐reported aesthetics and a reduction of the anxiety related to the appearance of the implant compared to baseline, with the CAF group obtaining significantly higher scores (p =.03 for both PROMs). Conclusions: CAF + CTG resulted in superior PSTD coverage outcomes, greater gain in KMW and MT, and better PROMs than TUN + CTG for the treatment of isolated PSTDs (ClinicalTrials.gov NCT03498911). [ABSTRACT FROM AUTHOR]

The structure of the Viologen‐Phenylene‐Imidazole (VPI) guest, previously shown to be bound by cucurbit[7]uril (CB[7]) with binding modes depending on pH and silver ions, has been extended by adding hydrophobic groups on the two extremities of VPI before investigations of CB[7] binding by NMR, ITC, X‐ray diffraction, UV‐vis and fluorescence spectroscopies. With an imidazole station extended by a naphthalene group (VPI‐N), binding modes of CB[7] are similar to those previously observed. However, with the viologen extended by a tolyl group (T‐VPI), CB[7] preferentially sits on station T, shuttling between the T and P stations at acid pH or after Ag+ addition. The CB[7] ⋅ T‐VPI complex thus behaves as a metal‐actuated thermodynamic stop‐and‐go molecular shuttle featured by fast and autonomous ring translocation between two stations and a continuum for fractional station occupancy solely and easily controlled by Ag+ concentration. [ABSTRACT FROM AUTHOR]

Introduction: Trials of CT‐based screening for lung cancer have shown a mortality advantage for screening in North America and Europe. Before introducing a nationwide lung cancer screening program in Germany, it is important to assess the criteria used in international trials in the German population. Methods: We used data from 3623 lung cancer patients from the data warehouse of the German Center for Lung Research (DZL). We compared the sensitivity of the following lung cancer screening criteria overall and stratified by age and histology: the National Lung Screening Trial (NLST), the Danish Lung Cancer Screening Trial (DLCST), the 2013 and 2021 US Preventive Services Task Force (USPSTF), and an adapted version of the Prostate, Lung, Colorectal, and Ovarian no race model (adapted PLCOm2012) with 6‐year risk thresholds of 1.0%/6 year and 1.7%/6 year. Results: Overall, the adapted PLCOm2012 model (1%/6 years), selected the highest proportion of lung cancer patients for screening (72.4%), followed by the 2021 USPSTF (70.0%), the adapted PLCOm2012 (1.7%/6 year) (57.4%), the 2013 USPTF (57.0%), DLCST criteria (48.7%), and the NLST (48.5%). The adapted PLCOm2012 risk model (1.0%/6 year) had the highest sensitivity for all histological types except for small‐cell and large‐cell carcinomas (non‐significant), whereas the 2021 USPTF selected a higher proportion of patients. The sensitivity levels were higher in males than in females. Conclusion: Using a risk‐based selection score resulted in higher sensitivities compared to criteria using dichotomized age and smoking history. However, gender disparities were apparent in all studied eligibility criteria. In light of increasing lung cancer incidences in women, all selection criteria should be reviewed for ways to close this gender gap, especially when implementing a large‐scale lung cancer screening program. [ABSTRACT FROM AUTHOR]

Objective: This study was designed to identify changes in the expression of proteins occurring during the progression of oral squamous cell carcinoma (OSCC) and to validate their impact on patient prognosis. Materials and Methods: The human OSCC cell line UPCI‐SCC‐040 was treated in vitro with TGF‐β1, and transcriptome analysis of differentially expressed genes (DEGs) revealed putative candidates relative to untreated cells. The respective protein expression levels of the most important genes were immunohistochemically validated on a tissue microarray (TMA) containing tissue samples from 39 patients with OSCC and were correlated with disease‐free survival (DFS) as the primary clinical endpoint. Results: Our univariate Cox proportional hazard regression (CR) analysis revealed significant correlations among positive N stage (local lymph node metastasis, p =.04), stearoyl‐CoA desaturase‐1 (p <.01), sclerostin (p =.01), and CD137L expression (p =.04) and DFS. Stearoyl‐CoA desaturase‐1 and sclerostin remained the main prognostic factors (p <.01) in the multiple CR model. Conclusion: We identified changes in differentially expressed genes during OSCC progression in vitro and translated the impact of the most deregulated genes on patient prognosis. Stearoyl‐CoA desaturase‐1 and sclerostin acted as independent prognostic factors in OSCC and could also be interesting candidates for new cancer targeted therapeutic approaches. [ABSTRACT FROM AUTHOR]

Background: As globalization of surgical training increases, growing evidence demonstrates a positive impact of global surgery experiences on trainees from high-income countries (HIC). However, few studies have assessed the impact of these largely unidirectional experiences from the perspectives of host surgical personnel from low- and middle-income countries (LMIC). This study aimed to assess the impact of unidirectional visitor involvement from the perspectives of host surgical personnel in Kijabe, Kenya. Methods: Voluntary semi-structured interviews were conducted with 43 host surgical personnel at a tertiary referral hospital in Kijabe, Kenya. Qualitative analysis was used to identify salient and recurring themes related to host experiences with visiting surgical personnel. Perceived benefits and challenges of HIC involvement and host interest in bidirectional exchange were assessed. Results: Benefits of visitor involvement included positive learning experiences (95.3%), capacity building (83.7%), exposure to diverse practices and perspectives (74.4%), improved work ethic (51.2%), shared workload (44.2%), access to resources (41.9%), visitor contributions to patient care (41.9%), and mentorship opportunities (37.2%). Challenges included short stays (86.0%), visitor adaptation and integration (83.7%), cultural differences (67.4%), visitors with problematic behaviors (53.5%), learner saturation (34.9%), language barriers (32.6%), and perceived power imbalances between HIC and LMIC personnel (27.9%). Nearly half of host participants expressed concerns about the lack of balanced exchange between HIC and LMIC programs (48.8%). Almost all (96.9%) host trainees expressed interest in a bidirectional exchange program. Conclusion: As the field of global surgery continues to evolve, further assessment and representation of host perspectives is necessary to identify and address challenges and promote equitable, mutually beneficial partnerships between surgical programs in HIC and LMIC. [ABSTRACT FROM AUTHOR]

Mo–Si–Ti alloys, like eutectic Mo–20Si–52.8Ti (at%), have previously been intensely investigated, owing to their excellent oxidation and creep resistance. To better understand high‐temperature mechanical behavior, a holistic assessment of microstructural features is necessary. Correspondingly, 3D‐focused ion beam tomography is carried out in Mo–20Si–52.8Ti. The results indicate a severely interconnected network of Mo solid solution (MoSS) and intermetallic (Ti,Mo)5Si3. Both phases retain similar network connectivity, lamellar sizes, etc. The brittle to ductile transition temperature (BDTT) is then determined through a series of bending tests and interpreted using the microstructural information. The BDTT is found to be ≈1100–1150 °C, different from Mo–9Si–8B with a continuous MoSS network. The BDTT is an immediate consequence of the continuous network of both MoSS and (Ti,Mo)5Si3. The MoSS network is instrumental in crack trapping and bridging, indicating that the present phase distribution maximized the mechanical performance over (Ti,Mo)5Si3. Having determined the network microstructure and BDTT, tensile creep behavior is evaluated and compared to previously published compressive creep results. The results show consistency in terms of strain rate, stress exponent, and microstructural features indicating a reliably good creep resistance for the network microstructure of Mo–20Si–52.8Ti regardless of loading direction. [ABSTRACT FROM AUTHOR]

The aim of the present study was to establish a modular platform of poly‐L‐lysine‐heparin (PLL‐Hep) polyelectrolyte multilayer (PEM) coatings on titanium surfaces for dual growth factor delivery of recombinant human bone morphogenic protein 2 (rhBMP2) and recombinant human vascular endothelial growth factor 165 (rhVEGF165) in clinically relevant quantities. Release characteristics for both growth factors differed significantly depending on film architecture. rhBMP2 induced activation of alkaline phosphatase in C2C12 cells and proliferation of human mesenchymal stem cells (hMSCs). rhVEGF mediated induction of von Willebrand factor (vWF) in hMSCs and proliferation of human umbilical vein endothelial cells. Osteogenic and angiogenic effects were modified by variation in cross‐linking and architecture of the PEMs. By creating multilayer films with distinct zones, release characteristics and proportion of both growth factor delivery could be tuned and surface‐activity modified to enhance angiogenic or osteogenic function in various ways. In summary, the system provides a modular platform for growth factor delivery that allows for individual composition and accentuation of angiogenic and osteogenic surface properties. [ABSTRACT FROM AUTHOR]

For individuals who have experienced tooth loss, dental implants are an important treatment option for oral reconstruction. For these patients, alveolar bone augmentation and acceleration of osseointegration optimize implant stability. Traditional oral surgery often requires invasive procedures, which can result in prolonged treatment time and associated morbidity. It has been previously shown that chemical vapor deposition (CVD) polymerization of functionalized [2.2]paracyclophanes can be used to anchor gene encoding vectors onto biomaterial surfaces and local delivery of a bone morphogenetic protein (BMP)‐encoding vector can increase alveolar bone volume and density in vivo. This study is the first to combine the use of CVD technology and BMP gene delivery on titanium for the promotion of bone regeneration and bone to implant contact in vivo. BMP‐7 tethered to titanium surface enhances osteoblast cell differentiation and alkaline phosphatase activity in vitro and increases alveolar bone regeneration and % bone to implant contact similar to using high doses of exogenously applied BMP‐7 in vivo. The use of this innovative gene delivery strategy on implant surfaces offers an alternative treatment option for targeted alveolar bone reconstruction. [ABSTRACT FROM AUTHOR]

Coarse‐grained composites of refractory ceramics and refractory metals are a novel approach for materials at application temperatures up to 1500 °C. Al2O3 and the refractory metals Nb and Ta are suitable candidates for enhanced thermal shock capability, as they show similar thermal expansion. During fabrication, a key aspect to consider is the possible formation of additional phases upon interaction of the constituent phases as well as through reaction with the environment. X‐Ray diffraction (XRD) and investigations of the microstructure with scanning electron microscopy methods unveil Al2O3–Nb composite to form NbO, whereas for Al2O3–Ta the ternary compound aluminum tantalate (AlTaO4) is found. Thermodynamic calculations show that the changing oxygen solubility in Nb accounts for the formation of NbO, and explain the absence of a corresponding niobate (AlNbO4) phase. AlTaO4 is identified as the disordered tetragonal high‐temperature modification. [ABSTRACT FROM AUTHOR]

The ease with which racemic mixtures crystallize compared with the equivalent chiral systems is routinely taken advantage of to produce crystals of small molecules. However, biological macromolecules such as DNA and proteins are naturally chiral, and thus the limited range of chiral space groups available hampers the crystallization of such molecules. Inspiring work over the past 15 years has shown that racemic mixtures of proteins, which were made possible by impressive advances in protein chemical synthesis, can indeed improve the success rate of protein crystallization experiments. More recently, the racemic crystallization approach was extended to include nucleic acids as a possible aid in the determination of enantiopure DNA crystal structures. Here, findings are reported that suggest that the benefits may extend beyond this. Two racemic crystal structures of the DNA sequence d(CCCGGG) are described which were found to fold into A‐form DNA. This form differs from the Z‐form DNA conformation adopted by the chiral equivalent in the solid state, suggesting that the use of racemates may also favour the emergence of new conformations. Importantly, the racemic mixture forms interactions in the solid state that differ from the chiral equivalent (including the formation of racemic pseudo‐helices), suggesting that the use of racemic DNA mixtures could provide new possibilities for the design of precise self‐assembled nanomaterials and nanostructures. [ABSTRACT FROM AUTHOR]

In large‐eddy simulations, subgrid‐scale (SGS) processes are parameterized as a function of filtered grid‐scale variables. First‐order, algebraic SGS models are based on the eddy‐viscosity assumption, which does not always hold for turbulence. Here we apply supervised deep neural networks (DNNs) to learn SGS stresses from a set of neighboring coarse‐grained velocity from direct numerical simulations of the convective boundary layer at friction Reynolds numbers Reτ up to 1243 without invoking the eddy‐viscosity assumption. The DNN model was found to produce higher correlation between SGS stresses compared to the Smagorinsky model and the Smagorinsky‐Bardina mixed model in the surface and mixed layers and can be applied to different grid resolutions and various stability conditions ranging from near neutral to very unstable. The DNN model can capture key statistics of turbulence in a posteriori (online) tests when applied to large‐eddy simulations of the atmospheric boundary layer. Plain Language Summary: Using grid‐scale state variables to represent subgrid‐scale (SGS) processes is a major step in large‐eddy simulations of turbulence, which typically rely on some physically based assumptions that do not always apply. Here we replace physically based assumptions with deep learning in SGS modeling and show the latter performs better in a priori (offline) tests of atmospheric turbulence. In addition, the deep neural networks model well captures key statistics of turbulence in a posteriori (online) tests when applied to in large‐eddy simulations of atmospheric boundary layers. Key Points: Deep learning‐based subgrid‐scale models outperform traditional eddy‐viscosity models in a priori (offline) testsDeep learning‐based subgrid‐scale models can account for density stratification effects in boundary‐layer turbulenceThe DNN model can capture key turbulence statistics in a posteriori (online) tests when applied to large‐eddy simulations of the atmospheric boundary layer [ABSTRACT FROM AUTHOR]

Double perovskites are considered for future photovoltaic and electro‐optic applications as a toxic‐free alternative to lead halide perovskites. Alas, due to the lower efficiency of lead‐free devices, material properties need to improve to compete. In this work, the self‐healing and annealing of crystal voids is reported. Experiments are conducted on nanocrystals and in situ a transmission electron microscopy (TEM) microscope. The setup enables creation of crystal voids and to monitor their dynamics in real time. Void trajectories and velocities are calculated for TEM videos. An inaccessible, protected volume for migration near the nanocrystal outer surface is discovered, confining the migration of voids to inner crystal parts. Once surface passivation in the form of organic ligands is removed, void dynamics changes, to enable annealing of the voids and self‐healing of the crystal. It is determined that surface ligand protection against void migration is extending several atomic layers below the crystal surface. Modeling based on these results predict equilibrium positions for the voids, which are discovered in the data. The study suggests that tuning of organic ligand density influences structural stability and crystal defect tolerance in double perovskites. Engineering surfaces with inherent self‐healing properties may increase efficiencies in future devices based on these materials. [ABSTRACT FROM AUTHOR]

The formation of a tetranuclear self‐assembled species constructed around a TiO4N2 motif is reported. This aggregate is generated from Ti(OiPr)4, 2,2'‐bipyrimidine (bpym) and a bis‐biphenol strand (L2H4) where two 2,2'‐biphenol units are connected with a biphenyl spacer. The solid‐state structure of the [Ti4(L2)4(bpym)4] architecture reveals the formation of an unprecedented chiral alternate [2×2] grid. In addition to the structural characterization of the [Ti4(L2)4(bpym)4] architecture, geometry optimisation on various possible isomeric tetrameric assemblies ([2×2] grid, alternate [2×2] grid, circular helicate or cyclic hemihelicate) is performed using DFT calculations. These results confirm the higher stability of the alternate [2×2] grid over the other possible tetranuclear isomers and allow examining the replacement of the bpym ligands by two novel diimine chelates within the tetranuclear assembly (2,2'‐bipyridine=bipy and 2,2'‐bipyrazine=bipyraz). From this initial theoretical investigation, the competition between these three nitrogen ligands in the course of the self‐assembly process is next evaluated. Overall, this investigation shows that the exclusive formation of the alternate [2×2] grid is driven by CH⋅⋅⋅N interactions. [ABSTRACT FROM AUTHOR]

Aim: To evaluate the efficacy of adjuvant, capacitive resistive monopolar radiofrequency (CRMRF, INDIBA) treatment at 448 kHz together with physiotherapeutic techniques compared to a sham treatment with the same techniques, for pain reduction and quality of life (QoL) improvements in patients with chronic pelvic pain syndrome (CPPS). Methods: A triple‐blind, randomized controlled trial (RCT) including patients with CPPS randomly allocated (1:1) to a CRMRF‐activated group (intervention) or a CRMRF‐deactivated one (control). Both groups received physiotherapeutic techniques and pain education weekly for 10 consecutive weeks. Data from a visual analogical scale and the SF‐12 questionnaire were collected at trial commencement and repeated at the 5th and 10th sessions. Pain intensity was considered the main outcome. For the comparisons between variables, the χ2 and Student's t test were used. Superiority was analyzed by estimating the mean change (95% confidence interval). Analysis was performed for the per‐protocol and the intention‐to‐treat populations. The statistical significance level was set at p < 0.05. Results: Eighty‐one patients were included (67.9% women) with a mean age of 43.6 years (SD 12.9). CRMRF lessened pain scores by more than 2 points and improved QoL by 5 points. There were no relevant side effects and overall adherence to the treatment was 86.4%. Conclusions: This is the first RCT that evaluates the efficacy of CRMRF (INDIBA) compared to a sham treatment, and demonstrates its superiority in decreasing pain and improving QoL. Such results may lead to greater prescribing of CRMRF when treating CPPS patients. [ABSTRACT FROM AUTHOR]

Lamellar structures of transition metal phosphorus trisulfides possess strong intralayer bonding, albeit adjacent layers are held by weak van der Waals interactions. Those compounds received enormous interest due to their unique combination of optical and long‐range magnetic properties. Among them, iron phosphorus trisulfide (FePS3) gathered special attention for being a semiconductor with an absorption edge in the near‐infrared, as well as showing an Ising‐like anti‐ferromagnetism. A successful growth of centimeter size bulk FePS3 crystals with a chemical yield above 70% is reported, whose crystallographic structure and composition are carefully identified by advanced electron microscopy methodologies, including atomic resolution elemental mapping, along with photoelectron spectroscopy. The knowledge on the optical activity of FePS3 is extended utilizing temperature‐dependent absorption and photoacoustic spectroscopies, while measurements are corroborated with density‐functional theory calculations. Temperature‐dependent experiments show a small and monotonic band‐edge energy shift down to 115 K and expose the interconnected importance of electron‐phonon coupling. Most of all, the correlation between the optical behavior and the magnetic phase transition is revealed, which shows the practical utilization of temperature‐dependent optical absorption to investigate magnetic interactions. [ABSTRACT FROM AUTHOR]

Near‐infrared spectroscopy (NIRS) allows innovative applications in terms of quality control, for example, in raw materials verification, in process analytical technology (PAT), and in discrimination between genuine and falsified medicines. The development of small and cheap handheld devices is expanding in the field, while trying to keep similar performances as benchtop instruments have. Considering traceability and quality control of drug compounds, this work is intended to identify 13 different paracetamol tablets on the Belgian market by using NIRS. The performances of a Fourier‐transform near‐infrared spectroscopy (FT‐NIR) benchtop and two handheld NIR spectrometers were investigated comparatively. All spectra were collected through the blister in the reflectance diffuse mode. NIR spectral fingerprints were pretreated and analyzed using principal component analysis (PCA) and classified with soft independent modeling of class analogy (SIMCA). The performances of the spectrometers were evaluated after standardization of the reference benchtop database to the handheld spectrometers. The instrumental response of the benchtop spectrometer was standardized towards the handheld device using the piecewise direct standardization (PDS) algorithm. These investigations permitted the advantages and limitations of NIR data standardization on predictive models to be pointed out. The SIMCA models based on the spectral data of the benchtop (B), handheld 1 (H1), and handheld 2 (H2) instruments had an accuracy of 99.2%, 97.7%, and 96.2%, respectively. The same accuracy was obtained with the models of the transferred benchtop spectra for the H1 and H2 devices. However, adding handheld spectra to the transferred benchtop spectra resulted in models with improved accuracy: from 97.7% to 98.5% for the H1 instrument and from 96.2% to 97.7% for the H2 instrument. The proposed strategy highlights the potential of using a reference database collected by NIRS for pharmaceutical analyses by handheld NIR spectrometers in terms of traceability. The study presented in this work aimed to highlight the potential of handheld devices to discriminate pharmaceutical formulations, using a standardized reference database. [ABSTRACT FROM AUTHOR]

Objectives: To evaluate the relationship between gingival phenotype and tooth location based on selected index teeth ("Ramfjord") and assess possible differences between women and men. Material and Methods: Thirty‐six women and 20 men voluntarily participated in this investigation with an average age of 23 years (min: 19; max: 37). Gingival phenotypes (GP) were assessed by transparency of a periodontal probe through the buccal gingival margin. Results: A comparable and similar GP on all index teeth was only found in seven out of the 56 subjects, that is, thin or thick only: Five participants (three male/two female) showed a uniform and constantly thick and two females a constantly thin GP. While the majority of molars (94.6%; p = 0.006) showed a thick GP, premolars (61.6%; p = 0.09) as well as incisors (70.5%; p = 0.046) were predominantly categorized as thin. In addition, significantly thicker GP was in general observed for maxillary teeth (p = 0.001) but without differences between genders (p = 0.722). Conclusion: No constant GP can be expected within one dentition. The use of the "Ramfjord teeth" may serve as a quick overview and reliable method to screen GP distribution. [ABSTRACT FROM AUTHOR]

Desmoid fibromatosis (DF) is one of the rarest locally aggressive growing benign tumor entities. We present an overview of the literature and a rare clinical case of a 22‐year‐old female patient, who was diagnosed with aggressive DF in the left pharyngeal wall at the age of 4 years old. [ABSTRACT FROM AUTHOR]

The differentiation between a pulmonary metastasis and a newly developed squamous cell carcinoma of the lung in patients with prior head and neck squamous cell carcinoma (HNSCC) is difficult due to a lack of biomarkers but is crucially important for the prognosis and therapy of the affected patient. By using high‐resolution mass spectrometry in combination with stable isotope labelling by amino acids in cell culture, we identified 379 proteins that are differentially expressed in squamous cell carcinomas of the lung and the head and neck. Of those, CAV1, CAV2, LGALS1, LGALS7, CK19, and UGDH were tested by immunohistochemistry on 194 tissue samples (98 lung and 96 HNSCCs). The combination of CAV1 and LGALS7 was able to distinguish the origin of the squamous cell carcinoma with high accuracy (area under the curve 0.876). This biomarker panel was tested on a cohort of 12 clinically classified lung tumours of unknown origin after HNSCC. Nine of those tumours were immunohistochemically classifiable. [ABSTRACT FROM AUTHOR]

Aim: To test the hypothesis that the use of rhBMP2 in established defects requires additional growth factors such as rhVEGF to accomplish effective bone repair. Materials and Methods: Horizontal/vertical defects of 2 cm length and 1 cm height were created bilaterally in the alveolar crest of the maxillae of 18 minipigs together with the extraction of all premolar teeth and one molar tooth on both sides. After 3 months of healing, defects were augmented with 0.5 g particulate PDLLA/CaCO3 composite loaded with 400 µg rhBMP2/50 µg rhVEGF165 on one side and 800 µg rhBMP2 on the other in 12 test animals, whereas defects in six control animals were sham operated and left unfilled on one side and augmented with blank carriers on the other. After 4 and 13 weeks, the animals were evaluated each for area of new bone formation (mm²) and bone density (area %). Results: Augmentations with carriers loaded with 800 g µrhBMP2 failed to induce significantly more bone than in the augmentations with unloaded carrier after 4 and 13 weeks (p =.1000, p =.381). Augmentations with carriers loaded with 400 µg rhBMP2 and 50 µg erhVEGF165 resulted in significantly increased bone formation after 13 weeks (p =.024) compared to blank carriers. Soft tissue in augmentations with combined rhBMP2/rhVEGF165 loading exhibited numerous microvessels compared to soft tissue in augmentations with rhBMP2. Conclusions: It is concluded that effective bone regeneration in augmentations of established alveolar ridge defects may require the application of rhVEGF additionally to rhBMP2. [ABSTRACT FROM AUTHOR]

Summary: Fungi are considered to cause grapevine trunk diseases such as esca that result in wood degradation. For instance, the basidiomycete Fomitiporia mediterranea (Fmed) is overabundant in white rot, a key type of wood‐necrosis associated with esca. However, many bacteria colonize the grapevine wood too, including the white rot. In this study, we hypothesized that bacteria colonizing grapevine wood interact, possibly synergistically, with Fmed and enhance the fungal ability to degrade wood. We isolated 237 bacterial strains from esca‐affected grapevine wood. Most of them belonged to the families Xanthomonadaceae and Pseudomonadaceae. Some bacterial strains that degrade grapevine‐wood components such as cellulose and hemicellulose did not inhibit Fmed growth in vitro. We proved that the fungal ability to degrade wood can be strongly influenced by bacteria inhabiting the wood. This was shown with a cellulolytic and xylanolytic strain of the Paenibacillus genus, which displays synergistic interaction with Fmed by enhancing the degradation of wood structures. Genome analysis of this Paenibacillus strain revealed several gene clusters such as those involved in the expression of carbohydrate‐active enzymes, xylose utilization and vitamin metabolism. In addition, certain other genetic characteristics of the strain allow it to thrive as an endophyte in grapevine and influence the wood degradation by Fmed. This suggests that there might exist a synergistic interaction between the fungus Fmed and the bacterial strain mentioned above, enhancing grapevine wood degradation. Further step would be to point out its occurrence in mature grapevines to promote esca disease development. [ABSTRACT FROM AUTHOR]

Previous studies have shown that the human visual system can detect a face and elicit a saccadic eye movement toward it very efficiently compared to other categories of visual stimuli. In the first experiment, we tested the influence of facial expressions on fast face detection using a saccadic choice task. Face‐vehicle pairs were simultaneously presented and participants were asked to saccade toward the target (the face or the vehicle). We observed that saccades toward faces were initiated faster, and more often in the correct direction, than saccades toward vehicles, regardless of the facial expressions (happy, fearful, or neutral). We also observed that saccade endpoints on face images were lower when the face was happy and higher when it was neutral. In the second experiment, we explicitly tested the detection of facial expressions. We used a saccadic choice task with emotional‐neutral pairs of faces and participants were asked to saccade toward the emotional (happy or fearful) or the neutral face. Participants were faster when they were asked to saccade toward the emotional face. They also made fewer errors, especially when the emotional face was happy. Using computational modeling, we showed that this happy face advantage can, at least partly, be explained by perceptual factors. Also, saccade endpoints were lower when the target was happy than when it was fearful. Overall, we suggest that there is no automatic prioritization of emotional faces, at least for saccades with short latencies, but that salient local face features can automatically attract attention. [ABSTRACT FROM AUTHOR]

Aim: To compare the efficacy of the treatment with transcutaneous perineal electrostimulation versus intracavitary electrostimulation to reduce the frequency of urinary incontinence after radical prostatectomy and the impact on the quality of life (QoL). Methods: This single‐blind equivalence‐randomized controlled trial equally (1:1) randomly allocated men with urinary incontinence post radical prostatectomy into surface electrodes perineal group (intervention group, IG) and intra‐anal probe group (control group, CG). Outcomes included changes in the 24h‐Pad Test (main variable), and ICIQ‐SF (International Consultation on Incontinence Questionnaire Short‐Form), SF‐12 (Short Form Health Survey), and I‐QOL (incontinence quality of life questionnaire) questionnaires. Clinical data were collected at baseline, 6 and 10 weeks. For the comparisons between variables, χ2 test and Student's t test were used. Equivalence was analyzed by estimating the mean change (90% confidence interval) of urinary incontinence based on the Pad Test. The analysis was performed for the per‐protocol and the intention‐to‐treat populations. Statistical significance level was set at p < 0.05. Results: Seventy patients were included, mean age 62.8 (SD 9.4) years. Mean baseline 24h‐Pad Test was 328.3 g (SD 426.1) and a significant decrease (p < 0.001) in the grams of urine loss at 5 weeks (159.1 g in the IG and 121.7 g in the CG), and at 10 weeks of treatment (248.5 g in the IG and 235.8 g in the CG) was observed. However, the final difference in the grams of urine loss between both treatments showed the absence of statistical significance (p = 0.874). In both groups, the ICIQ‐SF, I‐QOL, and SF‐12 questionnaires revealed a significant improvement in QoL. Conclusion: Surface and intra‐anal electrostimulation treatments reduced significantly losses of urine, but differences in grams of urine loss throughout the therapy between groups were not significant, suggesting that the efficacy of the two treatments is not statistically different. Nonetheless, the improvement observed in both groups was statistically significant and clinically relevant. [ABSTRACT FROM AUTHOR]

Diversification of the structures and the applications possible for foldamers rely on expansion of the building block library available for their synthesis. In this work, we describe the synthesis of a range of three dimensional heteroaromatic monomers, based on iptycene scaffolds, that are suitable for the synthesis of aromatic oligoamide foldamers. These units can be obtained in gram quantities in up to 80 % yield through [4+2] cycloaddition between diester, diamine, and amino acid derivatives of 1,8‐diazaanthracenes and a variety of dienophiles. X‐ray structural studies of the monomers and an oligomer show that the new motif orients the two heterocyclic rings and attached groups at an angle of approximately 120° to each other, opening new geometric considerations for the design of this class of foldamer. [ABSTRACT FROM AUTHOR]

After extensive studies of 1D and 2D skeletal carbo‐mers based on C8 π‐conjugating dialkynylbutatriene units (DABs: ∼C≡C−(R)C=C=C=C(R)−C≡C∼) bridging sp or sp2 centers in carbo‐butene, carbo‐xylylene or carbo‐benzene derivatives, 3D versions are envisaged through carbo‐barrelenes and partially reduced derivatives thereof where two or three DAB blades span a bridge between sp3 carbinol vertices or ether thereof. For R=Ph, stable representatives were synthesized through a pivotal [6]pericyclynedione, and extensively characterized by spectroscopic, electrochemical and crystallographic methods. Density functional theory calculations allow detailed analysis of structural and electronic features of the 7 Å high C26 barrel‐shaped molecules, and show that they can behave as cages for ionic species. Beyond aesthetical concerns, the results could open prospects of applications in host‐guest supramolecular chemistry and single molecule charge transport. [ABSTRACT FROM AUTHOR]

Refractory high entropy alloys (RHEA) are considered as novel promising high‐temperature materials for structural applications at ultrahigh temperatures primarily due to their attractive mechanical properties. By contrast, the oxidation behavior of RHEA has raised concern owing to pest oxidation, significant weight changes, scale spallation, or even complete oxidation at elevated temperatures. Herein, the currently available literature on high‐temperature oxidation behavior of RHEA is reviewed with respect to alloy composition, mass changes, corrosion products, and scale constitution. While many RHEA indeed suffer from poor oxidation resistance similar to that of pure refractory metals, some RHEA exhibit very good protectiveness, which is attributed to the formation of either well‐known protective scales such as α‐Al2O3 or rarely encountered complex oxides such as CrTaO4. Thermodynamic and kinetic aspects of oxide formation and growth are discussed to understand the oxidation mechanisms typical of RHEA. Further research directions with respect to additional in‐depth studies elucidating the oxidation mechanisms as well as the further consequent improvement of the oxidation resistance of RHEA are developed from the current intermediate stage of research in the field. [ABSTRACT FROM AUTHOR]

The simultaneous optimization of device efficiency, stability and large area processing represents one of the biggest challenges to exploit the potential offered by polymer solar cells. In this context, detailed studies of the impact of different interlayers on the key device properties are of crucial importance. Herein, the thermal stability of inverted polymer solar cells containing two different metal oxides as an anode interlayer is compared: i) ≈80 nm of solution‐processed tungsten oxide (WOx) and, ii) 10 nm of (thermally evaporated) molybdenum oxide (MoOx) as a reference system. A detailed comparison focused on the evolution of device performances/properties before and after thermal stress (85°C for 140 h in dark) is reported, highlighting advantages arising from the use of WOx as an interlayer. Two sets of inverted solar cells, based on either HBG‐1:PC61BM and P3HT:PC61BM as active layer, are fabricated and studied. Electrical, morphological and optical characterizations, performed both on freshly prepared and aged devices, are analyzed and correlated to explain the positive effect of the WOx interlayer on the resulting device thermal stability. Compared to fresh devices, thermally aged WOx (MoOx) based HBG‐1:PC61BM and P3HT:PC61BM solar cells exhibit an efficiency decay of −16% (−24%) and −28% (−57%), respectively. [ABSTRACT FROM AUTHOR]

The design and synthesis of a novel rotaxane/foldaxane hybrid architecture is reported. The winding of an aromatic oligoamide helix host around a dumbbell‐shaped thread‐like guest, or axle, already surrounded by a macrocycle was evidenced by NMR spectroscopy and X‐ray crystallography. The process proved to depend on the position of the macrocycle along the axle and the associated steric hindrance. The macrocycle thus behaves as a switchable shield that modulates the affinity of the helix for the axle. Reciprocally, the foldamer helix acts as a supramolecular auxiliary that compartmentalizes the axle. In some cases, the macrocycle is forced to move along the axle to allow the foldamer to reach its best recognition site. [ABSTRACT FROM AUTHOR]

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The orchestration of ever larger conformational changes is made possible by the development of increasingly complex foldamers. Aromatic sheets, a rare motif in synthetic foldamer structures, have been designed so as to form discrete stacks of intercalated aromatic strands through the self‐assembly of two identical subunits. Ion‐mobility ESI‐MS confirms the formation of compact dimers. X‐ray crystallography reveals the existence of two distinct conformational dimeric states that require large changes to interconvert. Molecular dynamics simulation validates the stability of the two conformations and the possibility of their interconversion. [ABSTRACT FROM AUTHOR]

Composite peening is a novel process to introduce ceramic blasting particles into the surface of substrates. Depending on the process parameters, the penetration depth of the blasting particles can be several micrometers. In previous investigations by some of the authors, it has been found that the ceramic particles incorporated during composite peening are significantly smaller compared to 10 μm in size before peening. Herein, the microstructure after composite peening is highlighted. To investigate this microstructure, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) are performed. The subsequent X‐ray diffraction (XRD) analysis provides further evidence of a severely deformed, nanocrystalline ceramic layer consisting of fragmented blasting particles. [ABSTRACT FROM AUTHOR]

Aim: To compare the efficacy of transcutaneous tibial nerve stimulation (TTNS) with percutaneous tibial nerve stimulation (PTNS) regarding patient‐reported outcomes measures, specifically quality‐of‐life (QoL) improvement and patient's treatment benefit, on symptoms associated with overactive bladder (OAB). Methods: Patients with refractory OAB symptoms and detrusor overactivity were randomized to receive TTNS or PTNS for 12 weeks. Data from self‐report OAB questionnaire short form (q‐SF) and incontinence (I)‐QoL questionnaires were collected pretreatment and at Weeks 6 and 12. Patients' self‐perceived benefits on symptoms (treatment benefit scale, TBS) were also gathered. Mean change in scores within and between groups were estimated. Results: Sixty‐eight adult patients (67.6% women) were included in the intention to treat analysis. Of those, 61 completed all questionnaires and were analyzed as per protocol. Statistically significant improvements in OAB‐q‐SF and I‐QoL between baseline and end‐of‐treatment scores were observed in both TTNS and PTNS groups (p <.001), being the differences much higher than the minimal important difference in both questionnaires. The scores of the OAB‐q‐SF scales (symptoms bother and health‐related QoL) showed no statistically significant differences between the two groups. Similarly, the differences regarding the I‐QoL questionnaire were statistically nonsignificant either (p =.607). When assessing the treatment benefit on symptoms, TBS responses between groups showed no statistical differences. Conclusion: A significant improvement of QoL was observed in both TTNS and PTNS groups. However, no patient‐reported outcomes measures scores support a difference between the two groups. Therefore, these findings along with TTNS ease of application and less invasiveness may lead to an increased indication of this technique for OAB. [ABSTRACT FROM AUTHOR]

A multicomponent self‐assembly reaction involving a bis‐biphenolato ligand (LH4), a 2,2'‐bipyrimidine chelate substituted by two (anthryl)vinyl moieties (bAnt) and Ti(OiPr)4 was investigated. An assembly {[Ti3(L)3(bAnt)3]}, composed of three homochiral TiO4N2 nodes, was characterized as being the thermodynamically‐end product. The crystal structure of this circular helicate highlighted an absence of symmetry for this compact compound. DOSY 1H NMR indicated that the nuclearity observed in the solid state for [Ti3(L)3(bAnt)3] was maintained in solution. An intermediate formulated as [Ti4(L)4(bAnt)4] was isolated. The structural analysis revealed that [Ti4(L)4(bAnt)4] was a symmetrical circular hollow helicate composed of four homochiral metallovertices. This study, supported by DFT calculation, brought some evidences on the sequences and the reasons leading to the symmetry decrease for this self‐assembly process. [ABSTRACT FROM AUTHOR]

Aerial parts containing cannabidiol can be purchased in a legal way but cannabis used as recreational drug is illegal in most European countries. Δ9‐tetrahydrocannabinol is one of the main cannabinoids responsible for the psychotropic effect. European Union countries and Switzerland authorize a concentration of THC of 0.2 % and 1.0 % w/w, respectively, for smoking products and industrial hemp. Public health inspectors and law enforcement officers need to check the legality of samples. Therefore there is a need for innovative approaches, allowing quality control of these products in an easy way and preferably on site. In many countries, cultivation of industrial hemp is permitted if the THC content does not exceed 0.2 % w/w. A portable equipment could be a useful measuring tool for farmers to check for the THC content at regular time. In this work, 189 samples were analysed with a benchtop and a handheld NIR device in order to create two classification methods according to European and Swiss laws. All samples were also analysed by GC‐FID to determine their THC concentration. Supervised analysis was applied in order to establish the best model. For the first classification, the accuracy was 91% for the test set with the benchtop data and 93 % for the test set with the handheld data. For the second classification, the accuracies were respectively 91 % and 95 %. The obtained models, hyphenating spectroscopic techniques and chemometrics, enable to discriminate legal and illegal cannabis samples according to European and Swiss laws. [ABSTRACT FROM AUTHOR]

Foldamers combining aliphatic and aromatic main-chain units often produce atypical structures that cannot easily be accessed from purely aromatic or aliphatic sequences. We report solidstate evidence that sequences comprising α-amino acids and quinoline-based monomers adopt conformations that combine the folding propensities of both components. Foldamers 2 and 3 having an XQQ repeat motif (X=α-amino acid, Q=quinoline) were synthesized. Crystals of 2 (X=Phe, Q with an anionic side chain) obtained from water revealed an aromatic helix where amide groups belonging to the α-amino acids created a hydrogen-bond array typical of peptidic helices. Crystals of 3 (X=Ser, Q with a lipophilic side chain) obtained from organic solvents revealed a helix-turn-helix structure in which α-amino acid side chains interfere with main-chain hydrogen bonding. High sequence-dependency of the conformation is typical of peptides but is shown here to include aromatic folding features. [ABSTRACT FROM AUTHOR]

Herein, the effect of water vapor on the oxidation resistance of the alloy Mo‐20Si‐52.8Ti (at%) is investigated. The alloy is oxidized in dry, wet, as well as in in situ changing atmospheres at 1100 °C. The oxidation kinetics changes from nearly parabolic to linear if water vapor is present in oxidizing atmosphere. Under all conditions, the oxide scales consist of an outer TiO2 and a TiO2SiO2 duplex layer underneath. In wet atmosphere, the thicknesses of the two regions substantially increase indicating a severe ingress of water vapor. The inferior oxidation resistance in wet environment is primarily rationalized by the fast diffusion of H2O through SiO2. [ABSTRACT FROM AUTHOR]

The TAR DNA‐binding protein (TDP‐43) self‐assembles into prion‐like aggregates considered to be the structural hallmark of amyotrophic lateral sclerosis and frontotemporal dementia. Here, we use a combination of electron microscopy, X‐ray fiber diffraction, Fourier‐transform infrared spectroscopy analysis, and solid‐state NMR spectroscopy to investigate the molecular organization of different TDP constructs, namely the full‐length TDP‐43 (1–414), two C‐terminal fragments [TDP‐35 (90–414) and TDP‐16 (267–414)], and a C‐terminal truncated fragment (TDP‐43 ∆GaroS2), in their fibrillar state. Although the different protein constructs exhibit similar fibril morphology and a typical cross‐β signature by X‐ray diffraction, solid‐state NMR indicates that TDP‐43 and TDP‐35 share the same polymorphic molecular structure, while TDP‐16 encompasses a well‐ordered amyloid core. We identified several residues in the so‐called C‐terminal GaroS2 (368–414) domain that participates in the rigid core of TDP‐16 fibrils, underlining its importance during the aggregation process. Our findings demonstrate that C‐terminal fragments can adopt a different molecular conformation in isolation or in the context of the full‐length assembly, suggesting that the N‐terminal domain and RRM domains play an important role in the TDP‐43 amyloid transition. [ABSTRACT FROM AUTHOR]

The recognition of either homomeric or heteromeric pairs of pentoses in an aromatic oligoamide double helical foldamer capsule was evidenced by circular dichroism (CD), NMR spectroscopy, and X‐ray crystallography. The cavity of the host was predicted to be large enough to accommodate simultaneously two xylose molecules and to form a 1:2 complex (one container, two saccharides). Solution and solid‐state data revealed the selective recognition of the α‐4C1‐d‐xylopyranose tautomer, which is bound at two identical sites in the foldamer cavity. A step further was achieved by sequestering a heteromeric pair of pentoses, that is, one molecule of α‐4C1‐d‐xylopyranose and one molecule of β‐1C4‐d‐arabinopyranose despite the symmetrical nature of the host and despite the similarity of the guests. Subtle induced‐fit and allosteric effects are responsible for the outstanding selectivities observed. [ABSTRACT FROM AUTHOR]