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Abstract Background Cisplatin (CDDP) remains a key agent in the treatment of muscle-infiltrating bladder carcinoma (MIBC). However, a proportion of MIBC patients do not respond to chemotherapy, which may be caused by the increased repair of CDDP-induced DNA damage. The purpose of this study was to explore the prognostic value of proteins involved in nucleotide excision repair (NER) and translesion DNA synthesis (TLS) in MIBC patients. Methods This is a retrospective analysis of 86 MIBC patients. The XPA, XPF, XPG, ERCC1, POLI, POLH and REV3L proteins were stained in primary bladder tumors and their levels were analyzed both in the total cohort and in a subgroup with metastatic urothelial carcinoma (mUC) that received gemcitabine and CDDP as a first-line therapy. Both cohorts were divided by percentage of cancer cells stained positive for each protein into subgroups with high and low expression. In the same manner, the combined expression of NER (XPA + ERCC1 + XPF + XPG) and TLS (POLI + POLH + REV3L), as the whole pathways, was analyzed. Results Mortality was 89.5% at the median follow-up of 120.2 months. In the total cohort, patients with tumors stained positive for XPA, XPG and POLI had significantly worse overall survival (OS) compared to those with negative staining [hazard ratio (HR) = 0.60, 0.62 and 0.53, respectively]. Both XPG and POLI were independent prognostic factors in multivariate analyses (MVA). In addition, an increase in NER and TLS pathway expression was significantly associated with worse OS in the total cohort (HR = 0.54 and 0.60, respectively). In the mUC subgroup, high POLI expression was associated with significant deterioration of OS (HR = 0.56) in univariate analyses, and its independent prognostic value was shown in MVA. Conclusions Our study showed significant correlations between the tumor expression of XPG and POLI, as well as NER and TLS as the whole pathways, and inferior OS. Hence, they could constitute prognostic biomarkers and potentially promising therapeutic targets in MIBC. However, a prospective trial is required for further validation, thereby overcoming the limitations of this study.

Abstract Background Germ cell tumours (GCTs) represent a highly curable malignity as they respond well to cisplatin (CDDP)-based chemotherapy. Nevertheless, a small proportion of GCT patients relapse or do not respond to therapy. As this might be caused by an increased capacity to repair CDDP-induced DNA damage, identification of DNA repair biomarkers predicting inadequate or aberrant response to CDDP, and thus poor prognosis for GCT patients, poses a challenge. The objective of this study is to examine the expression levels of the key nucleotide excision repair (NER) factors, XPA, ERCC1 and XPF, in GCT patients and cell lines. Methods Two hundred seven GCT patients’ specimens with sufficient follow-up clinical-pathological data and pairwise combinations of CDDP-resistant and -sensitive GCT cell lines were included. Immunohistochemistry was used to detect the ERCC1, XPF and XPA protein expression levels in GCT patients’ specimen and Western blot and qRT-PCR examined the protein and mRNA expression levels in GCT cell lines. Results GCT patients with low XPA expression had significantly better overall survival than patients with high expression (hazard ratio = 0.38, 95% confidence interval: 0.12–1.23, p = 0.0228). In addition, XPA expression was increased in the non-seminomatous histological subtype, IGCCCG poor prognosis group, increasing S stage, as well as the presence of lung, liver and non-pulmonary visceral metastases. Importantly, a correlation between inadequate or aberrant CDDP response and XPA expression found in GCT patients was also seen in GCT cell lines. Conclusions XPA expression is an additional independent prognostic biomarker for stratifying GCT patients, allowing for improvements in decision-making on treatment for those at high risk of refractoriness or relapse. In addition, it could represent a novel therapeutic target in GCTs.

Adolescence is a period of profound biopsychosocial development, with pubertally-driven neural reorganization as social demands increase in peer contexts. The explosive increase in social media access has fundamentally changed peer interactions among youth, creating an urgent need to understand its impact on neurobiological development and mental health. Extant literature indicates that using social media promotes social comparison and feedback seeking (SCFS) behaviors in youth, which portend increased risk for mental health disorders, but little is known about its impact on neurobiological development. We assessed social media behaviors, mental health symptoms, and spontaneous cortical activity using magnetoencephalography (MEG) in 80 typically developing youth (8–16 years) and tested how self-reported pubertal stage moderates their relationship. More mature adolescents who engaged in more SCFS showed weaker fusiform/parahippocampal alpha and medial prefrontal beta activity, and increased symptoms of anxiety and attention problems. Engaging in SCFS on social media during adolescence may thus relate to developmental differences in brain regions that undergo considerable development during puberty. These results are consistent with works indicating altered neurodevelopmental trajectories within association cortices surrounding the onset of many mental health disorders. Importantly, later pubertal stages may be most sensitive to the detrimental effects of social media use.

The flying agility demonstrated by dragonflies is accomplished by means of complex aerodynamic forces produced by flapping their four wings arranged in a tandem configuration. The current study presents a novel tandem flapping wing mechanism for a biomimetic air vehicle that was designed and manufactured to experimentally investigate the aerodynamic forces. By optimizing the configuration and using spatial network analysis, it is shown that the designed structure can flap the wings in a linear up–down stroke motion and is capable of maintaining good consistency and aerodynamic performance. Such a mechanism could be used in a future biomimetic micro air vehicle (BMAV) design. The mechanism uses an electromagnetic actuator to flap the wings with a variable beat frequency (30–210 Hz) at various angles of attack (−10°–20°). The results show that the tandem wings generate approximately 50% higher lift than the forewing or hindwing pairs acting alone. Tandem wings also improve stability, which could potentially allow hovering.

Abstract In magnetic systems, spin and exchange disorder can provide access to quantum criticality, frustration, and spin dynamics, but broad tunability of these responses and a deeper understanding of strong limit disorder are lacking. Here, it is demonstrated that high entropy oxides present a previously unexplored route to designing materials in which the presence of strong local compositional disorder may be exploited to generate tunable magnetic behaviors—from macroscopically ordered states to frustration‐driven dynamic spin interactions. Single‐crystal La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 films are used as a model system hosting a magnetic sublattice with a high degree of microstate disorder in the form of site‐to‐site spin and exchange type inhomogeneity. A classical Heisenberg model simplified to represent the highest probability microstates well describes how compositionally disordered systems can paradoxically host magnetic uniformity and demonstrates a path toward continuous control over ordering types and critical temperatures. Model‐predicted materials are synthesized and found to possess an incipient quantum critical point when magnetic ordering types are designed to be in direct competition, this leads to highly controllable exchange bias behaviors previously accessible only in intentionally designed bilayer heterojunctions.

Purpose Obesity can make bone marrow biopsy using manual landmarks as guidance technically challenging. This retrospective review was performed to assess the safety and technical success of performing bone marrow biopsies with computed tomography (CT)–guidance in obese patients. Materials and Methods This single-institution, retrospective study included 1,016 CT-guided bone marrow biopsies performed between 2009 and 2016. Thirty-four percent (n = 348) were performed in patients with a body mass index (BMI) of 30 kg/m2 or greater, and 7% (n = 75) were performed in patients with a BMI greater than 40 kg/m2. Demographic information, BMI, and complications were reviewed. The primary endpoint was technical success and procedurally related hemorrhagic complication. The electronic medical record was reviewed to identify procedural related hemorrhagic complications, Common Terminology Criteria for Adverse Events (CTCAE) Grade 3 or above. The complication rates in obese patients were compared with patients with a BMI less than 30 kg/m2. Results Biopsy was successfully performed in all patients. No biopsies resulted in a CTCAE Grade 3 or above complication. There was no difference in complication rate (0%) based on BMI. For patients with a BMI < 30 kg/m2, BMI ≥ 30 kg/m2, and BMI > 40 kg/m2, complications rates were 0% (95% confidence interval [CI]: 0–0.4%), 0% (95% CI: 0–0.9%), and 0% (95% CI: 0–4%), respectively. Conclusions CT-guided bone marrow biopsy in obese patients can be performed with a high rate of technical success and is safe. If patient body habitus limits the ability to palpate physical landmarks needed to perform bone marrow biopsy without image guidance, CT-guided bone marrow biopsy should be considered.

The interface between magnetic materials and topological insulators can drive the formation of exotic phases of matter and enable functionality through the manipulation of the strong spin polarized transport. Here, we report that the transport processes that rely on strong spin-momentum locking in the topological insulator Bi2Se3 are completely suppressed by scattering at a heterointerface with the kagome-lattice paramagnet, Co7Se8. Bi2Se3–Co7Se8–Bi2Se3 trilayer heterostructures were grown using molecular beam epitaxy, where magnetotransport measurements revealed a substantial suppression of the weak antilocalization effect for Co7Se8 at thicknesses as thin as a monolayer, indicating a strong dephasing mechanism. Bi2−xCoxSe3 films, in which Co is in a non-magnetic 3+ state, show weak antilocalization that survives to higher than x = 0.4, which, in comparison with the heterostructures, suggests that the unordered moments of Co2+ act as a far stronger dephasing element. This work highlights several important points regarding coherent transport processes involving spin-momentum locking in topological insulator interfaces and how magnetic materials can be integrated with topological materials to realize both exotic phases and novel device functionality.

A new class of ceramics, called entropy stabilized oxides, High Entropy Oxides (HEOs), multicomponent oxides, compositionally complex oxides, or polycation oxides, has generated considerable research interest since the first report in 2015. This multicomponent approach has created new opportunities for materials design and discovery. This Perspective will highlight some current research developments and possible applications while also providing an overview of the many successfully synthesized HEO systems to date. The polycation approach to composition development will be discussed along with a few case studies, challenges, and future possibilities afforded by this novel class of materials.

Phase competition in correlated oxides offers tantalizing opportunities as many intriguing physical phenomena occur near the phase transitions. Owing to a sharp metal-insulator transition (MIT) near room temperature, the correlated vanadium dioxide (VO2) exhibits a strong competition between insulating and metallic phases, which is important for practical applications. However, the phase boundary undergoes a strong modification when strain is involved, yielding complex phase transitions. Here, we report the emergence of nanoscale M2 phase domains in VO2 epitaxial films under anisotropic strain relaxation. The competing phases of the films are imaged by multilength-scale probes, detecting the structural and electrical properties in individual local domains. Competing evolution of the M1 and M2 phases indicates the critical role of lattice-strain on both the stability of the M2 Mott phase and the energetics of the MIT in VO2 films. This study demonstrates how strain engineering can be utilized to design phase states, which allow deliberate control of MIT behavior at the nanoscale in epitaxial VO2 films.

Micrometer-tall vertically aligned single-crystalline CoFe2O4 nanobrush architectures with extraordinarily large aspect ratio have been achieved by the precise control of a kinetic and thermodynamic non-equilibrium pulsed laser epitaxy process. Direct observations by scanning transmission electron microscopy reveal that the nanobrush crystal is mostly defect-free by nature, and epitaxially connected to the substrate through a continuous 2D interface layer. In contrast, periodic dislocations and lattice defects such as anti-phase boundaries and twin boundaries are frequently observed in the 2D interface layer, suggesting that interface misfit strain relaxation under a non-equilibrium growth condition plays a critical role in the self-assembly of such artificial architectures. Magnetic property measurements have found that the nanobrushes exhibit a saturation magnetization value of 6.16 B/f.u., which is much higher than the bulk value. The discovery not only enables insights into an effective route for fabricating unconventional high-quality nanostructures, but also demonstrates a novel magnetic architecture with potential applications in nanomagnetic devices.

Flap endonuclease 1 (FEN1) is a structure selective endonuclease required for proficient DNA replication and the repair of DNA damage. Cellularly active inhibitors of this enzyme have previously been shown to induce a DNA damage response and, ultimately, cell death. High-throughput screens of human cancer cell-lines identify colorectal and gastric cell-lines with microsatellite instability (MSI) as enriched for cellular sensitivity to N-hydroxyurea series inhibitors of FEN1, but not the PARP inhibitor olaparib or other inhibitors of the DNA damage response. This sensitivity is due to a synthetic lethal interaction between FEN1 and MRE11A, which is often mutated in MSI cancers through instabilities at a poly(T) microsatellite repeat. Disruption of ATM is similarly synthetic lethal with FEN1 inhibition, suggesting that disruption of FEN1 function leads to the accumulation of DNA double-strand breaks. These are likely a result of the accumulation of aberrant replication forks, that accumulate as a consequence of a failure in Okazaki fragment maturation, as inhibition of FEN1 is toxic in cells disrupted for the Fanconi anemia pathway and post-replication repair. Furthermore, RAD51 foci accumulate as a consequence of FEN1 inhibition and the toxicity of FEN1 inhibitors increases in cells disrupted for the homologous recombination pathway, suggesting a role for homologous recombination in the resolution of damage induced by FEN1 inhibition. Finally, FEN1 appears to be required for the repair of damage induced by olaparib and cisplatin within the Fanconi anemia pathway, and may play a role in the repair of damage associated with its own disruption.

Due to the limit in computing power arising from the Von Neumann bottleneck, computational devices are being developed that mimic neuro-biological processing in the brain by correlating the device characteristics with the synaptic weight of neurons. This platform combines ionic liquid gating and electrowetting for programmable placement/connectivity of the ionic liquid. In this platform, both short-term potentiation (STP) and long-term potentiation (LTP) are realized via electrostatic and electrochemical doping of the amorphous indium gallium zinc oxide (aIGZO), respectively, and pulsed bias measurements are demonstrated for lower power considerations. While compatible with resistive elements, we demonstrate a platform based on transitive amorphous indium gallium zinc oxide (aIGZO) pixel elements. Using a lithium based ionic liquid, we demonstrate both potentiation (decrease in device resistance) and depression (increase in device resistance), and propose a 2D platform array that would enable a much higher pixel count via Active Matrix electrowetting.

Abstract: A class of dynamical systems associated to rings of S-integers in rational function fields is described. General results about these systems give a rather complete description of the well-known dynamics in one-dimensional additive cellular automata with prime alphabet, including simple formulæ for the topological entropy and the number of periodic configurations. For these systems the periodic points are uniformly distributed along some subsequence with respect to the maximal measure, and in particular are dense. Periodic points may be constructed arbitrarily close to a given configuration, and rationality of the dynamical zeta function is characterized. Throughout the emphasis is to place this particular family of cellular automata into the wider context of S-integer dynamical systems, and to show how the arithmetic of rational function fields determines their behaviour. Using a covering space the dynamics of additive cellular automata are related to a form of hyperbolicity in completions of rational function fields. This expresses the topological entropy of the automata directly in terms of volume growth in the covering space.

Fanconi anemia (FA) is a devastating genetic disease, associated with genomic instability and defects in DNA interstrand cross-link (ICL) repair. The FA repair pathway is not thought to be conserved in budding yeast, and although the yeast Mph1 helicase is a putative homolog of human FANCM, yeast cells disrupted for MPH1 are not sensitive to ICLs. Here, we reveal a key role for Mph1 in ICL repair when the Pso2 exonuclease is inactivated. We find that the yeast FANCM ortholog Mph1 physically and functionally interacts with Mgm101, a protein previously implicated in mitochondrial DNA repair, and the MutSα mismatch repair factor (Msh2-Msh6). Co-disruption of MPH1, MGM101, MSH6, or MSH2 with PSO2 produces a lesion-specific increase in ICL sensitivity, the elevation of ICL-induced chromosomal rearrangements, and persistence of ICL-associated DNA double-strand breaks. We find that Mph1-Mgm101-MutSα directs the ICL-induced recruitment of Exo1 to chromatin, and we propose that Exo1 is an alternative 5'-3' exonuclease utilised for ICL repair in the absence of Pso2. Moreover, ICL-induced Rad51 chromatin loading is delayed when both Pso2 and components of the Mph1-Mgm101-MutSα and Exo1 pathway are inactivated, demonstrating that the homologous recombination stages of ICL repair are inhibited. Finally, the FANCJ- and FANCP-related factors Chl1 and Slx4, respectively, are also components of the genetic pathway controlled by Mph1-Mgm101-MutSα. Together this suggests that a prototypical FA-related ICL repair pathway operates in budding yeast, which acts redundantly with the pathway controlled by Pso2, and is required for the targeting of Exo1 to chromatin to execute ICL repair.

The envenomation syndrome of Redback spider bites, lactrodectism, is distinctive. However diagnosis can be difficult due to an atypical presentation. We describe the case of a 1 year old boy with irritability, diaphoresis and reduced oral intake, in whom a diagnosis was made of redback spider bite. Successful resolution of symptoms was achieved following treatment with antivenom. The symptoms and management of redback spider bites is discussed.

Abstract Pediatric obesity rates have quadrupled in the United States, and deficits in higher-order cognition have been linked to obesity, though it remains poorly understood how deviations from normal body mass are related to the neural dynamics serving cognition in youth. Herein, we determine how age- and sex-adjusted measures of body mass index (zBMI) scale with neural activity in brain regions underlying fluid intelligence. Seventy-two youth aged 9–16 years underwent high-density magnetoencephalography while performing an abstract reasoning task. The resulting data were transformed into the time-frequency domain and significant oscillatory responses were imaged using a beamformer. Whole-brain correlations with zBMI were subsequently conducted to quantify relationships between zBMI and neural activity serving abstract reasoning. Our results reveal that participants with higher zBMI exhibit attenuated theta (4–8 Hz) responses in both the left dorsolateral prefrontal cortex and left temporoparietal junction, and that weaker temporoparietal responses scale with slower reaction times. These findings suggest that higher zBMI values are associated with weaker theta oscillations in key brain regions and altered performance during an abstract reasoning task. Thus, future investigations should evaluate neurobehavioral function during abstract reasoning in youth with more severe obesity to identify the potential impact.

Despite effective antiretroviral therapy, cognitive impairment remains prevalent among people with HIV (PWH) and decrements in executive function are particularly prominent. One component of executive function is cognitive flexibility, which integrates a variety of executive functions to dynamically adapt one's behavior in response to changing contextual demands. Though substantial work has illuminated HIV-related aberrations in brain function, it remains unclear how the neural oscillatory dynamics serving cognitive flexibility are affected by HIV-related alterations in neural functioning. Herein, 149 participants (PWH: 74; seronegative controls: 75) between the ages of 29–76 years completed a perceptual feature matching task that probes cognitive flexibility during high-density magnetoencephalography (MEG). Neural responses were decomposed into the time-frequency domain and significant oscillatory responses in the theta (4–8 Hz), alpha (10–16 Hz), and gamma (74–98 Hz) spectral windows were imaged using a beamforming approach. Whole-brain voxel-wise comparisons were then conducted on these dynamic functional maps to identify HIV-related differences in the neural oscillatory dynamics supporting cognitive flexibility. Our findings indicated group differences in alpha oscillatory activity in the cingulo-opercular cortices, and differences in gamma activity were found in the cerebellum. Across all participants, alpha and gamma activity in these regions were associated with performance on the cognitive flexibility task. Further, PWH who had been treated with antiretroviral therapy for a longer duration and those with higher current CD4 counts had alpha responses that more closely resembled those of seronegative controls, suggesting that optimal clinical management of HIV infection is associated with preserved neural dynamics supporting cognitive flexibility.

Background: The variety of innovations to traditional centre-based pulmonary rehabilitation (CBPR), including different modes of delivery and adjuncts, are likely to lead to differential responses in physical activity, sedentary behaviour and sleep. Objectives: To examine the relative effectiveness of different pulmonary rehabilitation-based interventions on physical activity, sedentary behaviour and sleep. Methods: Randomised trials in chronic respiratory disease involving pulmonary rehabilitation-based interventions were systematically searched for. Network meta-analyses compared interventions for changes in physical activity, sedentary behaviour and sleep in COPD. Results: 46 studies were included, and analyses were performed on most common outcomes: steps per day (k=24), time spent in moderate-to-vigorous physical activity (MVPA; k=12) and sedentary time (k=8). There were insufficient data on sleep outcomes (k=3). CBPR resulted in greater steps per day and MVPA and reduced sedentary time compared to usual care. CBPR+physical activity promotion resulted in greater increases in steps per day compared to both usual care and CBPR, with greater increases in MVPA and reductions in sedentary time compared to usual care, but not CBPR. Home-based pulmonary rehabilitation resulted in greater increases in steps per day and decreases in sedentary time compared to usual care. Compared to usual care, CBPR+physical activity promotion was the only intervention where the lower 95% confidence interval for steps per day surpassed the minimal important difference. No pulmonary rehabilitation-related intervention resulted in greater increases in MVPA or reductions in sedentary time compared to CBPR. Conclusion: The addition of physical activity promotion to pulmonary rehabilitation improves volume of physical activity, but not intensity, compared to CBPR. High risk of bias and low certainty of evidence suggests that these results should be viewed with caution.

Numerous investigations have characterized the oscillatory dynamics serving working memory in adults, but few have probed its relationship with chronological age in developing youth. We recorded magnetoencephalography during a modified Sternberg verbal working memory task in 82 youth participants aged 6–14 years old. Significant oscillatory responses were identified and imaged using a beamforming approach and the resulting whole-brain maps were probed for developmental effects during the encoding and maintenance phases. Our results indicated robust oscillatory responses in the theta (4–7 Hz) and alpha (8–14 Hz) range, with older participants exhibiting stronger alpha oscillations in left-hemispheric language regions. Older participants also had greater occipital theta power during encoding. Interestingly, there were sex-by-age interaction effects in cerebellar cortices during encoding and in the right superior temporal region during maintenance. These results extend the existing literature on working memory development by showing strong associations between age and oscillatory dynamics across a distributed network. To our knowledge, these findings are the first to link chronological age to alpha and theta oscillatory responses serving working memory encoding and maintenance, both across and between male and female youth; they reveal robust developmental effects in crucial brain regions serving higher order functions.

Rationale There is conflicting evidence whether aerobic exercise training (AET) reduces pulse wave velocity (PWV) in adults with and without long-term conditions (LTCs).Objective To explore whether PWV improves with AET in adults with and without LTC, to quantify the magnitude of any effect and understand the influence of the exercise prescription.Data sources CENTRAL, MEDLINE and EMBASE were among the databases searched.Eligibility criteria We included studies with a PWV measurement before and after supervised AET of at least 3 weeks duration. Exclusion criteria included resistance exercise and alternative measures of arterial stiffness.Design Controlled trials were included in a random effects meta-analysis to explore the effect of AET on PWV. Uncontrolled studies were included in a secondary meta-analysis and meta-regression exploring the effect of patient and programme factors on change in PWV. The relevant risk of bias tool was used for each study design.Results 79 studies (n=3729) were included: 35 controlled studies (21 randomised control trials (RCT) (n=1240) and 12 non-RCT (n=463)) and 44 uncontrolled (n=2026). In the controlled meta- analysis, PWV was significantly reduced following AET (mean (SD) 11 (7) weeks) in adults with and without LTC (mean difference −0.63; 95% CI −0.82 to −0.44; p

This study investigates the prediction of supervisee burnout and secondary traumatic stress by perceived supervisor servant leadership. Authors hypothesized that the servant leadership of supervisors would predict diminished burnout and secondary traumatic stress of supervisees. A sample of 241 counseling supervisees participated in the cross-sectional study and completed instruments measuring burnout, secondary traumatic stress, and perceived servant leadership of their direct supervisors. Data were analyzed with two simple linear regressions, and a one-way MANOVA was performed to determine if supervisee burnout, supervisee secondary traumatic stress, and perceived servant leadership of supervisors differed significantly according to supervisor type (i.e., clinical, administrative, or dual role). Results confirmed the main hypothesis, and administrative supervisors were perceived to demonstrate significantly less servant leadership qualities than the other two supervisor types. Limitations, avenues for future research, and implications for counselor education and supervision are discussed.

Abstract Development of promising new materials for above room temperature magnetic cooling applications relies on careful balancing of structure and composition to maximize accessible metastable phases that can drive a strong magnetocaloric effect (MCE). However, the working temperatures of these materials may fall outside of desired application windows. In this work, it is shown that it is possible to control metastable phase stability temperatures of Fe5Si3 through selection of appropriate spin and charge doping. Here, the parent material's desired structure appears only within a narrow temperature range from 1098 to 1303 K. Doping with Mn and P is shown to allow stabilization of the parent's high temperature phase and resulting MCE to room temperature. The structural and magnetic properties, and the magnetocaloric effect of single crystal Fe4.83Mn0.16Si2.91P0.09 (FMSP) are investigated experimentally and theoretically. A first‐order magneto‐elastic transition is observed at 348 K, where magnetic onset is accompanied by a change in lattice volume without an apparent change in crystal symmetry. Although the trace Mn and P doping are found to decrease the TC, the maximum magnetic entropy change ΔSMax(T) and the relative cooling power (RCP) of FMSP are enhanced compared to polycrystalline Fe5Si3. As a result, an intrinsically broader entropy change over a larger temperature span is generated in the lightly doped single crystal of Fe5Si3. The magnetic moment of the system is also enhanced. Density functional theory (DFT) calculations are performed to gain microscopic insights into the experimental findings. The results suggest that the hexagonal Fe5Si3 is a new giant room temperature MCE material that is on par with La–Fe–Si and Fe‐Mn‐P‐Si systems.

Magnetic interfaces and the phenomena arising from them drive both the design of modern spintronics and fundamental research. Recently, it was revealed that through designing magnetic frustration in configurationally complex entropy stabilized oxides, exchange bias can occur in structurally single crystal films. This eliminates the need for complex heterostructures and nanocomposites in the design and control of magnetic response phenomena. In this work, we demonstrate through hole doping of a high entropy perovskite oxide that tuning of magnetic responses can be achieved. With detailed magnetometry, we show magnetic coupling exhibiting a variety of magnetic responses including exchange bias and antiferromagnetic spin reversal in the entropy stabilized ABO3 perovskite oxide La1−xSrx(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 family. We find that manipulation of the A-site charge state can be used to balance magnetic phase compositions and coupling responses. This allows for the creation of highly tunable exchange bias responses. In the low Sr doping regime, a spin frustrated region arising at the antiferromagnetic phase boundary is shown to directly couple to the antiferromagnetic moments of the film and emerges as the dominant mechanism, leading to a vertical shift of magnetization loops in response to field biasing. At higher concentrations, direct coupling of antiferromagnetic and ferromagnetic regions is observed. This tunability of magnetic coupling is discussed within the context of these three competing magnetic phases, revealing critical features in designing exchange bias through exploiting spin frustration and disorder in high entropy oxides.

Abstract Engineering oxygen vacancy formation and distribution is a powerful route for controlling the oxygen sublattice evolution that affects diverse functional behavior. The controlling of the oxygen vacancy formation process is particularly important for inducing topotactic phase transitions that occur by transformation of the oxygen sublattice. Here we demonstrate an epitaxial nanocomposite approach for exploring the spatial control of topotactic phase transition from a pristine perovskite phase to an oxygen vacancy-ordered brownmillerite (BM) phase in a model oxide La0.7Sr0.3MnO3 (LSMO). Incorporating a minority phase NiO in LSMO films creates ultrahigh density of vertically aligned epitaxial interfaces that strongly influence the oxygen vacancy formation and distribution in LSMO. Combined structural characterizations reveal strong interactions between NiO and LSMO across the epitaxial interfaces leading to a topotactic phase transition in LSMO accompanied by significant morphology evolution in NiO. Using the NiO nominal ratio as a single control parameter, we obtain intermediate topotactic nanostructures with distinct distribution of the transformed LSMO-BM phase, which enables systematic tuning of magnetic and electrical transport properties. The use of self-assembled heterostructure interfaces by the epitaxial nanocomposite platform enables more versatile design of topotactic phase structures and correlated functionalities that are sensitive to oxygen vacancies.

High entropy oxides are emerging as an exciting new avenue to design highly tailored functional behaviors that have no traditional counterparts. Study and application of these materials are bringing together scientists and engineers from physics, chemistry, and materials science. The diversity of each of these disciplines comes with perspectives and jargon that may be confusing to those outside of the individual fields, which can result in miscommunication of important aspects of research. In this Perspective, we provide examples of research and characterization taken from these different fields to provide a framework for classifying the differences between compositionally complex oxides, high entropy oxides, and entropy stabilized oxides, which is intended to bring a common language to this emerging area. We highlight the critical importance of understanding a material’s crystallinity, composition, and mixing length scales in determining its true definition.

Annotation of surgical video is important for establishing ground truth in surgical data science endeavors that involve computer vision. With the growth of the field over the last decade, several challenges have been identified in annotating spatial, temporal, and clinical elements of surgical video as well as challenges in selecting annotators. In reviewing current challenges, we provide suggestions on opportunities for improvement and possible next steps to enable translation of surgical data science efforts in surgical video analysis to clinical research and practice.

Cycloalkenes are bulk petrochemicals that are currently obtained from fossil fuels. Here, the authors developed multi enzyme pathways in combination with a Ru-catalyzed metathesis reaction for the one-pot production of cyclopentene, cyclohexene, and cycloheptene from olive oil-derived intermediates.

Olefin metathesis is one of the most powerful C–C double-bond-forming reactions. Metathesis reactions have had a tremendous impact in organic synthesis, enabling a variety of applications in polymer chemistry, drug discovery and chemical biology. Although challenging, the possibility to perform aqueous metatheses has become an attractive alternative, not only because water is a more sustainable medium, but also to exploit biocompatible conditions. This review focuses on the progress made in aqueous olefin metatheses and their applications in chemical biology.

Artificial enzymes can be used to elicit reactions in cells. Here, the authors developed such an artificial catalyst combined with a genetic switch, and showed that it was readily taken up by human cells and able to kick off a reaction cascade resulting in the biosynthesis of the desired product.

Abstract The synthesis of a diseleno[3,2‐b:2′,3′‐d]selenophene (DSS) composed of three fused selenophenes is reported and it is used as a building block for the preparation of a high hole mobility conjugated polymer (PDSSTV). The polymer demonstrates strong intermolecular interactions even in solution, despite steric repulsion between the large Se atom in DSS and adjacent (Cβ)–H atoms which leads to a partially twisted confirmation PDSSTV. Nevertheless, 2D grazing incidence X‐ray diffraction (2D‐GIXD) analysis reveals that the polymer tends to align in a highly ordered edge‐on orientation after thermal annealing. The polymer demonstrates promising performance in a field‐effect transistor device with saturated hole mobility up to 2 cm2 V−1 s−1 obtained under relatively low gate voltages of −30 V. The ultilization of a Se‐containing fused aromatic system, therefore, appears to be a promising avenue for the development of high‐performance conjugated polymers.

Whilst superlattices containing thin films of 5d transition metal oxides are expected to yield strong interfacial coupling, only weak effects have been observed. Here, the authors report strong coupling between 3d SrMnO3 and 5d SrIrO3due to the interplay of strong Coulomb and spin orbit interactions.

Herein we report on a 96-well plate assay based on the fluorescence resulting from the ring-closing metathesis of two profluorophoric substrates. To demonstrate the validity of the approach, four commercially available ruthenium-metathesis catalysts were evaluated in six different solvents. The results from the fluorescent assay agree well with HPLC conversions, validating the usefulness of the approach.

The objective of molecular systems engineering is to move beyond functional components and primary systems, towards cumulate emergent properties in interfaced higher-order systems of unprecedented multifunctionality and sophistication.

In a multi-disciplinary team effort we gather experts on light-to-chemical energy conversion, artificial metalloenzymes, and bio-inspired polymer vesicles in order to construct molecular factories which produce added-value chemicals in an overall process fueled by solar energy. We outline our long-term vision and discuss specific challenges associated with this endeavor.