Iodination of carbohydrate-derived 1,2-oxazines to enantiopure 5-iodo-3,6 -dihydro-2H-1,2-oxazines and subsequent palladium-catalyzed cross-coupling reactions

Iodination of carbohydrate-derived 3,6-dihydro-2H-1,2-oxazines of type 3 using iodine and pyridine in DMF furnished 5-iodo-substituted 1,2-oxazine derivatives 4 with high efficacy. The alkenyl iodide moiety of 1,2-oxazine derivatives syn-4 and anti-4 was subsequently exploited for the introduction of new functionalities at the C-5 position by applying palladium-catalyzed carbon–carbon bond-forming reactions such as Sonogashira, Heck, or Suzuki coupling reactions as well as a cyanation reaction. These cross-coupling reactions led to a series of 5-alkynyl-, 5-alkenyl-, 5-aryl- and 5-cyano- substituted 1,2-oxazine derivatives being of considerable interest for further synthetic elaborations. This was exemplarily demonstrated by the hydrogenation of syn-21 and anti-24 and by a click reaction of a 5-alkynyl-substituted precursor

Colloquium: Spin-orbit effects in superconducting hybrid structures

Spin-orbit coupling (SOC) describes the interaction between an electron's motion and its spin, and is ubiquitous in condensed matter systems. The interplay of SOC with superconductivity has attracted significant interest over the past decade and understanding has substantially progressed, both experimentally and theoretically. Even with well-understood materials, conventional $s$-wave superconducting hybrid structures with SOC provide a platform for realizing exotic phenomena and counterparts in the normal state. Understanding the emergent phenomena in such systems is an important aim in condensed matter physics. One such area relates to the generation and interplay of spin-polarized spin-triplet Cooper pairs in superconducting structures with magnetic interfaces. It is established that certain forms of magnetic inhomogeneity at an $s$-wave superconductor interface with a ferromagnet can transform spin-singlet Cooper pairs into a spin-polarized spin-triplet Cooper pairs, enabling transformative concepts for cryogenic computing. Recently, theory and experiments have demonstrated singlet-to-triplet pair conversion via SOC in $s$-wave superconducting structures with or without magnetic layers. Moreover, the spin-dependent properties of quasiparticles and their non-equilibrium behavior also change in the presence of SOC. These breakthroughs create the potential for energy-efficient control of static and dynamic spin phenomena in superconducting structures and devices. This article reviews progress in superconducting spintronics with a focus on the coupling of superconductivity and SOC in hybrid structures and devices, and outlines directions that are critical for future device development and fundamental understanding.Comment: 34 pages, 14 figure

Fos regulates macrophage infiltration against surrounding tissue resistance by a cortical actin-based mechanism in Drosophila

The infiltration of immune cells into tissues underlies the establishment of tissue-resident macrophages and responses to infections and tumors. Yet the mechanisms immune cells utilize to negotiate tissue barriers in living organisms are not well understood, and a role for cortical actin has not been examined. Here, we find that the tissue invasion of Drosophila macrophages, also known as plasmatocytes or hemocytes, utilizes enhanced cortical F-actin levels stimulated by the Drosophila member of the fos proto oncogene transcription factor family (Dfos, Kayak). RNA sequencing analysis and live imaging show that Dfos enhances F-actin levels around the entire macrophage surface by increasing mRNA levels of the membrane spanning molecular scaffold tetraspanin TM4SF, and the actin cross-linking filamin Cheerio, which are themselves required for invasion. Both the filamin and the tetraspanin enhance the cortical activity of Rho1 and the formin Diaphanous and thus the assembly of cortical actin, which is a critical function since expressing a dominant active form of Diaphanous can rescue the Dfos macrophage invasion defect. In vivo imaging shows that Dfos enhances the efficiency of the initial phases of macrophage tissue entry. Genetic evidence argues that this Dfos-induced program in macrophages counteracts the constraint produced by the tension of surrounding tissues and buffers the properties of the macrophage nucleus from affecting tissue entry. We thus identify strengthening the cortical actin cytoskeleton through Dfos as a key process allowing efficient forward movement of an immune cell into surrounding tissues

molecular recognition at interfaces

In order to investigate molecular recognition on surfaces, an azide- functionalized monolayer was deposited on gold. The monolayer was characterized by X-ray photoelectron spectroscopy (XPS) and angle-resolved near-edge X-ray absorption fine structure (NEXAFS) experiments and the decomposition of the azide upon irradiation with X-ray beams was investigated. Subsequently, various alkyne-functionalized host and guest molecules were attached to the azide by 1,3-dipolar cycloaddition. These modified surfaces and their host–guest chemistry were analysed by XPS and angle-resolved NEXAFS. The reversibility of guest binding was shown for one example as a proof of principle

Discordance rates of biopsy techniques among men with prostate cancer that are candidates for active surveillance

Q1Q1e887-e887INTRODUCTION AND OBJECTIVES: With the ongoing stage migration in the diagnosis of prostate cancer, there has been increased interest in management with active surveillance. Our study examines the ability of two prostate biopsy techniques to predict appropriate candidates for active surveillance.METHODS500 consecutive patients, between 2005 and 2007, that underwent trans-rectal ultrasound guided biopsy by either an office biopsy with 12 cores or a saturation biopsy with ≥18 cores, and subsequent radical prostatectomy were identified. Using criteria of: Gleason score ≤6, clinical stage T1 or T2a, Prostate Specific Antigen (PSA) <10 and ≤33% of cores involved, 220 patients were found to be candidates for active surveillance. Pathology results from the prostatectomy specimens were used determine the discordance rate of each biopsy technique.RESULTSOf the 220 candidates for active surveillance, 124 patients underwent an office biopsy with 12 cores, and 96 patients underwent a saturation biopsy. The median number of cores in the saturation biopsy cohort was 27. There was no statistically significant difference between the groups in terms of median age (p=0.18), pre-operative PSA (p=0.48) and clinical stage (p=0.2). At least one previous negative biopsy had been performed on 20 patients (16%) in the office cohort and 43 patients (45%) in the saturation cohort (p= <0.001). In the 12 core biopsy group, 17 patients (14%) were upgraded to Gleason 7 on pathology from the prostatectomy specimen. In the saturation biopsy group, 14 patients (15%) were upgraded to Gleason 7, and 1 patient (1%) was upgraded to Gleason 8. There was no statistically significant difference in the rate of upgrading between the office and saturation biopsy cohorts (p=0.69). In the office biopsy group, 2 patients (1.6%) were upstaged to pT3 disease, compared to 0 patients (0%) in the saturation biopsy group (p=0.58). No statistically significant difference in the estimated tumor volume of the prostatectomy specimen was seen between the cohorts (p=0.47).CONCLUSIONSCandidates for active surveillance can accurately be predicted with 12 core biopsies. In both cohorts, approximately 1 in 6 patients underwent upgrading based on the pathology of the prostatectomy specimen

Spintronics: Fundamentals and applications

Spintronics, or spin electronics, involves the study of active control and manipulation of spin degrees of freedom in solid-state systems. This article reviews the current status of this subject, including both recent advances and well-established results. The primary focus is on the basic physical principles underlying the generation of carrier spin polarization, spin dynamics, and spin-polarized transport in semiconductors and metals. Spin transport differs from charge transport in that spin is a nonconserved quantity in solids due to spin-orbit and hyperfine coupling. The authors discuss in detail spin decoherence mechanisms in metals and semiconductors. Various theories of spin injection and spin-polarized transport are applied to hybrid structures relevant to spin-based devices and fundamental studies of materials properties. Experimental work is reviewed with the emphasis on projected applications, in which external electric and magnetic fields and illumination by light will be used to control spin and charge dynamics to create new functionalities not feasible or ineffective with conventional electronics.Comment: invited review, 36 figures, 900+ references; minor stylistic changes from the published versio

Correction to: Two years later: Is the SARS-CoV-2 pandemic still having an impact on emergency surgery? An international cross-sectional survey among WSES members

Background: The SARS-CoV-2 pandemic is still ongoing and a major challenge for health care services worldwide. In the first WSES COVID-19 emergency surgery survey, a strong negative impact on emergency surgery (ES) had been described already early in the pandemic situation. However, the knowledge is limited about current effects of the pandemic on patient flow through emergency rooms, daily routine and decision making in ES as well as their changes over time during the last two pandemic years. This second WSES COVID-19 emergency surgery survey investigates the impact of the SARS-CoV-2 pandemic on ES during the course of the pandemic. Methods: A web survey had been distributed to medical specialists in ES during a four-week period from January 2022, investigating the impact of the pandemic on patients and septic diseases both requiring ES, structural problems due to the pandemic and time-to-intervention in ES routine. Results: 367 collaborators from 59 countries responded to the survey. The majority indicated that the pandemic still significantly impacts on treatment and outcome of surgical emergency patients (83.1% and 78.5%, respectively). As reasons, the collaborators reported decreased case load in ES (44.7%), but patients presenting with more prolonged and severe diseases, especially concerning perforated appendicitis (62.1%) and diverticulitis (57.5%). Otherwise, approximately 50% of the participants still observe a delay in time-to-intervention in ES compared with the situation before the pandemic. Relevant causes leading to enlarged time-to-intervention in ES during the pandemic are persistent problems with in-hospital logistics, lacks in medical staff as well as operating room and intensive care capacities during the pandemic. This leads not only to the need for triage or transferring of ES patients to other hospitals, reported by 64.0% and 48.8% of the collaborators, respectively, but also to paradigm shifts in treatment modalities to non-operative approaches reported by 67.3% of the participants, especially in uncomplicated appendicitis, cholecystitis and multiple-recurrent diverticulitis. Conclusions: The SARS-CoV-2 pandemic still significantly impacts on care and outcome of patients in ES. Well-known problems with in-hospital logistics are not sufficiently resolved by now; however, medical staff shortages and reduced capacities have been dramatically aggravated over last two pandemic years

The genetic architecture of the human cerebral cortex

The cerebral cortex underlies our complex cognitive capabilities, yet little is known about the specific genetic loci that influence human cortical structure. To identify genetic variants that affect cortical structure, we conducted a genome-wide association meta-analysis of brain magnetic resonance imaging data from 51,665 individuals. We analyzed the surface area and average thickness of the whole cortex and 34 regions with known functional specializations. We identified 199 significant loci and found significant enrichment for loci influencing total surface area within regulatory elements that are active during prenatal cortical development, supporting the radial unit hypothesis. Loci that affect regional surface area cluster near genes in Wnt signaling pathways, which influence progenitor expansion and areal identity. Variation in cortical structure is genetically correlated with cognitive function, Parkinson's disease, insomnia, depression, neuroticism, and attention deficit hyperactivity disorder

The Essential Elements of a Risk Governance Framework for Current and Future Nanotechnologies

Societies worldwide are investing considerable resources into the safe development and use of nanomaterials. Although each of these protective efforts is crucial for governing the risks of nanomaterials, they are insufficient in isolation. What is missing is a more integrative governance approach that goes beyond legislation. Development of this approach must b