Imidazolium-based titanosilicate nanospheres as active catalysts in carbon dioxide conversion:Towards a cascade reaction from alkenes to cyclic carbonates

Porous silica-based nanospheres bearing titanium centres as single site were successfully synthesized employing a time- and energy-efficient procedure. The influence of the post-synthesis treatment on the insertion of Ti was investigated via DR UV-Vis and XPS spectroscopy and the titanium content was quantified through ICP-OES analysis. The textural and structural properties of the different solids were evaluated via XRD, TEM and N2 physisorption. The resulting materials were thereafter covalently functionalized with imidazolium chloride, followed by characterization via 29Si and 13C solid-state NMR, N2 physisorption and chemical combustion analysis. The bi-functional catalysts were tested in the challenging conversion of CO2 with cyclohexene oxide to the corresponding cyclic carbonate as well as with various other epoxides with excellent results. The insertion of Ti as single site played a key role substantially improving the activity of the solids. The most active bi-functional material was successfully recovered and reused through multiple cycle without loss of the catalytic activity. Moreover, the cyclohexene epoxidation reaction was tested as well employing the mono-functionalized Ti-based material. The catalytic mixture, composed by the mono-functional and bi-functional solids, was efficiently used to convert the cyclohexene into cyclohexene oxide and subsequently the cyclohexene oxide into the corresponding carbonate thus opening the prospect for a cascade reaction

Nonlinear optical diode effect in a magnetic Weyl semimetal

Weyl semimetals have emerged as a promising quantum material system to discover novel electrical and optical phenomena, due to their combination of nontrivial quantum geometry and strong symmetry breaking. One crucial class of such novel transport phenomena is the diode effect, which is of great interest for both fundamental physics and modern technologies. In the electrical regime, giant electrical diode effect (the nonreciprocal transport) has been observed in Weyl systems. In the optical regime, novel optical diode effects have been theoretically considered but never probed experimentally. Here, we report the observation of the nonlinear optical diode effect (NODE) in the magnetic Weyl semimetal CeAlSi, where the magnetic state of CeAlSi introduces a pronounced directionality in the nonlinear optical second-harmonic generation (SHG). By physically reversing the beam path, we show that the measured SHG intensity can change by at least a factor of six between forward and backward propagation over a wide bandwidth exceeding 250 meV. Supported by density-functional theory calculations, we establish the linearly dispersive bands emerging from Weyl nodes as the origin of the extreme bandwidth. Intriguingly, the NODE directionality is directly controlled by the direction of magnetization. By utilizing the electronically conductive semimetallic nature of CeAlSi, we demonstrate current-induced magnetization switching and thus electrical control of the NODE in a mesoscopic spintronic device structure with current densities as small as 5 kA/cm$^2$. Our results advance ongoing research to identify novel nonlinear optical/transport phenomena in magnetic topological materials. The NODE also provides a way to measure the phase of nonlinear optical susceptibilities and further opens new pathways for the unidirectional manipulation of light such as electrically controlled optical isolators.Comment: 28 pages, 12 figure

On supersymmetric quantum mechanics

This paper constitutes a review on N=2 fractional supersymmetric Quantum Mechanics of order k. The presentation is based on the introduction of a generalized Weyl-Heisenberg algebra W_k. It is shown how a general Hamiltonian can be associated with the algebra W_k. This general Hamiltonian covers various supersymmetrical versions of dynamical systems (Morse system, Poschl-Teller system, fractional supersymmetric oscillator of order k, etc.). The case of ordinary supersymmetric Quantum Mechanics corresponds to k=2. A connection between fractional supersymmetric Quantum Mechanics and ordinary supersymmetric Quantum Mechanics is briefly described. A realization of the algebra W_k, of the N=2 supercharges and of the corresponding Hamiltonian is given in terms of deformed-bosons and k-fermions as well as in terms of differential operators.Comment: Review paper (31 pages) to be published in: Fundamental World of Quantum Chemistry, A Tribute to the Memory of Per-Olov Lowdin, Volume 3, E. Brandas and E.S. Kryachko (Eds.), Springer-Verlag, Berlin, 200

Quantum metric nonlinear Hall effect in a topological antiferromagnetic heterostructure

Quantum geometry - the geometry of electron Bloch wavefunctions - is central to modern condensed matter physics. Due to the quantum nature, quantum geometry has two parts, the real part quantum metric and the imaginary part Berry curvature. The studies of Berry curvature have led to countless breakthroughs, ranging from the quantum Hall effect in 2DEGs to the anomalous Hall effect (AHE) in ferromagnets. However, in contrast to Berry curvature, the quantum metric has rarely been explored. Here, we report a new nonlinear Hall effect induced by quantum metric by interfacing even-layered MnBi2Te4 (a PT-symmetric antiferromagnet (AFM)) with black phosphorus. This novel nonlinear Hall effect switches direction upon reversing the AFM spins and exhibits distinct scaling that suggests a non-dissipative nature. Like the AHE brought Berry curvature under the spotlight, our results open the door to discovering quantum metric responses. Moreover, we demonstrate that the AFM can harvest wireless electromagnetic energy via the new nonlinear Hall effect, therefore enabling intriguing applications that bridges nonlinear electronics with AFM spintronics.Comment: 19 pages, 4 figures and a Supplementary Materials with 66 pages, 4 figures and 3 tables. Originally submitted to Science on Oct. 5, 202

Ultrasound imaging of apoptosis: high-resolution non-invasive monitoring of programmed cell death in vitro, in situ and in vivo

A new non-invasive method for monitoring apoptosis has been developed using high frequency (40 MHz) ultrasound imaging. Conventional ultrasound backscatter imaging techniques were used to observe apoptosis occurring in response to anticancer agents in cells in vitro, in tissues ex vivo and in live animals. The mechanism behind this ultrasonic detection was identified experimentally to be the subcellular nuclear changes, condensation followed by fragmentation, that cells undergo during apoptosis. These changes dramatically increase the high frequency ultrasound scattering efficiency of apoptotic cells over normal cells (25- to 50-fold change in intensity). The result is that areas of tissue undergoing apoptosis become much brighter in comparison to surrounding viable tissues. The results provide a framework for the possibility of using high frequency ultrasound imaging in the future to non-invasively monitor the effects of chemotherapeutic agents and other anticancer treatments in experimental animal systems and in patients. © 1999 Cancer Research Campaig

Non-surgical interventions for lumbar spinal stenosis leading to neurogenic claudication: a clinical practice guideline

Lumbar spinal stenosis (LSS) causing neurogenic claudication (NC) is increasingly common with an aging population and can be associated with significant symptoms and functional limitations. We developed this guideline to present the evidence and provide clinical recommendations on nonsurgical management of patients with LSS causing NC. Using the GRADE approach, a multidisciplinary guidelines panel based recommendations on evidence from a systematic review of randomized controlled trials and systematic reviews published through June 2019, or expert consensus. The literature monitored up to October 2020. Clinical outcomes evaluated included pain, disability, quality of life, and walking capacity. The target audience for this guideline includes all clinicians, and the target patient population includes adults with LSS (congenital and/or acquired, lateral recess or central canal, with or without low back pain, with or without spondylolisthesis) causing NC. The guidelines panel developed 6 recommendations based on randomized controlled trials and 5 others based on professional consensus, summarized in 3 overarching recommendations: (Grade: statements are all conditional/weak recommendations) Recommendation 1. For patients with LSS causing NC, clinicians and patients may initially select multimodal care nonpharmacological therapies with education, advice and lifestyle changes, behavioral change techniques in conjunction with home exercise, manual therapy, and/or rehabilitation (moderate-quality evidence), traditional acupuncture on a trial basis (very low-quality evidence), and postoperative rehabilitation (supervised program of exercises and/or educational materials encouraging activity) with cognitive-behavioral therapy 12 weeks postsurgery (low-quality evidence). Recommendation 2. In patients LSS causing NC, clinicians and patients may consider a trial of serotonin–norepinephrine reuptake inhibitors or tricyclic antidepressants. (very low-quality evidence). Recommendation 3. For patients LSS causing NC, we recommend against the use of the following pharmacological therapies: nonsteroidal anti-inflammatory drugs, methylcobalamin, calcitonin, paracetamol, opioids, muscle relaxants, pregabalin (consensus-based), gabapentin (very low-quality), and epidural steroidal injections (high-quality evidence). Perspective: This guideline, on the basis of a systematic review of the evidence on the nonsurgical management of lumbar spine stenosis, provides recommendations developed by a multidisciplinary expert panel. Safe and effective non-surgical management of lumbar spine stenosis should be on the basis of a plan of care tailored to the individual and the type of treatment involved, and multimodal care is recommended in most situations. © 2021 The Author

Incorporating non-equilibrium dynamics into demographic history inferences of a migratory marine species

ELC was supported while writing this paper by a EU Horizon 2020 Marie Slodowska Curie Fellowship, project BEHAVIOUR-CONNECT, by a Newton Fellowship from the Royal Society of London and Bayesian statistical training was supported by National Science Foundation (award DEB- 1145200). Laboratory analyses conducted by ELC were funded by a small grant from the British Ecological Society 5076 / 6118 and Bayesian analysis was supported by training from the National Science Foundation under Grant No. DEB-1145200. OEG was supported by the Marine Alliance for Science and Technology for Scotland (MASTS) funded by the Scottish Founding Council (grant reference HR09011). Genetic data from the South African right whale samples were generated by MB and PJP with the support of UC Berkeley, University of Stockholm and University of Groningen. Computational Biology analyses were supported by the University of St Andrews Bioinformatics Unit which is funded by a Wellcome Trust ISSF award.Understanding how dispersal and gene flow link geographically separated populations over evolutionary history is challenging, particularly in migratory marine species. In southern right whales (SRWs, Eubalaena australis), patterns of genetic diversity are likely influenced by the glacial climate cycle and recent history of whaling. Here we use a dataset of mitochondrial DNA (mtDNA) sequences (n=1,327) and nuclear markers (17 microsatellite loci, n=222) from major wintering grounds to investigate circumpolar population structure, historical demography, and effective population size. Analyses of nuclear genetic variation identify two population clusters that correspond to the South Atlantic and Indo-Pacific ocean basins that have similar effective breeder estimates. In contrast, all wintering grounds show significant differentiation for mtDNA, but no sex-biased dispersal was detected using the microsatellite genotypes. An approximate Bayesian computation (ABC) approach with microsatellite markers compared scenarios with gene flow through time, or isolation and secondary contact between ocean basins, while modeling declines in abundance linked to whaling. Secondary-contact scenarios yield the highest posterior probabilities, implying that populations in different ocean basins were largely isolated and came into secondary contact within the last 25,000 years, but the role of whaling in changes in genetic diversity and gene flow over recent generations could not be resolved. We hypothesis that these findings are driven by factors that promote isolation, such as female philopatry, and factors that could promote dispersal, such oceanographic changes. These findings highlight the application of ABC approaches to infer connectivity in mobile species with complex population histories and currently low levels of differentiation.PostprintPeer reviewe