Palladium-Catalyzed Oxidation of β-C(sp3)-H Bonds of Primary Alkylamines through a Rare Four-Membered Palladacycle Intermediate.

Site-selective functionalizations of C-H bonds are often achieved with a directing group that leads to five- or six-membered metallacyclic intermediates. Analogous reactions that occur through four-membered metallacycles are rare. We report a challenging palladium-catalyzed oxidation of primary C-H bonds β to nitrogen in an imine of an aliphatic amine, a process that occurs through a four-membered palladacyclc intermediate. The success of the reaction relies on the identification, by H/D exchange, of a simple directing group (salicylaldehyde) capable of inducing the formation of this small ring. To gain insight into the steps of the catalytic cycle of this unusual oxidation reaction, a series of mechanistic experiments and density functional theory (DFT) calculations were conducted. The experimental studies showed that cleavage of the C-H bond is rate-limiting and formation of the strained four-membered palladacycle is thermodynamically uphill. DFT calculations corroborated these conclusions and suggested that the presence of an intramolecular hydrogen bond between the oxygen of the directing group and hydroxyl group of the ligating acetic acid is crucial for stabilization of the palladacyclic intermediate

Symmetry, stability, and computation of degenerate lasing modes

We present a general method to obtain the stable lasing solutions for the steady-state ab initio lasing theory (SALT) for the case of a degenerate symmetric laser in two dimensions (2D). We find that under most regimes (with one pathological exception), the stable solutions are clockwise and counterclockwise circulating modes, generalizing previously known results of ring lasers to all 2D rotational symmetry groups. Our method uses a combination of semianalytical solutions close to lasing threshold and numerical solvers to track the lasing modes far above threshold. Near threshold, we find closed-form expressions for both circulating modes and other types of lasing solutions as well as for their linearized Maxwell-Bloch eigenvalues, providing a simple way to determine their stability without having to do a full nonlinear numerical calculation. Above threshold, we show that a key feature of the circulating mode is its “chiral” intensity pattern, which arises from spontaneous symmetry breaking of mirror symmetry, and whose symmetry group requires that the degeneracy persists even when nonlinear effects become important. Finally, we introduce a numerical technique to solve the degenerate SALT equations far above threshold even when spatial discretization artificially breaks the degeneracy.United States. Army Research Office. Institute for Soldier Nanotechnologies (Grant W911NF-07-D-0004)Austrian Science Fund (Project SFB NextLite F49-P10)United States. Air Force Research Laboratory (Agreement FA8650-15-2-5220

Controlling the radiation dynamics of MoSe2/WSe2 interlayer excitons via in-situ tuning the electromagnetic environment

We show that the spontaneous emission rate of the interlayer excitons in a twisted WSe2-MoSe2 heterobilayer can be precisely tailored in a low-temperature open optical microcavity via the Purcell effect. We engineer the local density of optical states in our resonator structures in two complementary experimental settings. In the first approach, we utilize an ultra-low quality factor planar vertical cavity structure, which develops multiple longitudinal modes that can be consecutively brought to resonance with the broad interlayer exciton spectrum of our heterostructure. Time-resolved photoluminescence measurements reveal that the interlayer exciton lifetime can thus be periodically tuned with an amplitude of around 100 ps. The resulting oscillations of the exciton lifetime allows us to extract a free-space radiative exciton lifetime of 2.2 ns and an approximately 15 % quantum efficiency of the interlayer excitons. We subsequently engineered the local density of optical states by introducing a spatially confined and fully spectrally tunable Tamm-plasmon resonance. The dramatic redistribution of the local optical modes in this setting allows us to encounter a profound inhibition of spontaneous emission of the interlayer excitons by a factor of 3.3. Our results will further boost the cavity-mediated collective emission phenomena such as super-radiance. We expect that specifically engineering the inhibition of radiation from moire excitons is a powerful tool to steer their thermalization, and eventually their condensation into coherent condensate phases.Comment: 16 pages, 3 figures, DFG SPP2244 fundings, et

The ICD-11 classification of personality disorders: a European perspective on challenges and opportunities

The 11th revision of the World Health Organization (WHO) International Classification of Diseases (ICD-11) includes a fundamentally new approach to Personality Disorders (PD). ICD-11 is expected to be implemented first in European countries before other WHO member states. The present paper provides an overview of this new ICD-11 model including PD severity classification, trait domain specifiers, and the additional borderline pattern specifier. We discuss the perceived challenges and opportunities of using the ICD-11 approach with particular focus on its continuity and discontinuity with familiar PD categories such as avoidant PD and narcissistic PD. The advent of the ICD-11 PD classification involves major changes for health care workers, researchers, administrators, and service providers as well as patients and families involved. The anticipated challenges and opportunities are put forward in terms of specific unanswered questions. It is our hope that these questions will stimulate further research and discussion among researchers and clinicians in the coming years

Towards harmonizing natural resources as an area of protection in life cycle impact assessment

Purpose. In this paper, we summarize the discussion and present the findings of an expert group effort under the umbrella of the United Nations Environment Programme (UNEP)/Society of Environmental Toxicology and Chemistry (SETAC) Life Cycle Initiative proposing natural resources as an Area of Protection (AoP) in Life Cycle Impact Assessment (LCIA). Methods: As a first step, natural resources have been defined for the LCA context with reference to the overall UNEP/SETAC Life Cycle Impact Assessment (LCIA) framework. Second, existing LCIA methods have been reviewed and discussed. The reviewed methods have been evaluated according to the considered type of natural resources and their underlying principles followed (use-to-availability ratios, backup technology approaches, or thermodynamic accounting methods). Results and discussion. There is currently no single LCIA method available that addresses impacts for all natural resource categories, nor do existing methods and models addressing different natural resource categories do so in a consistent way across categories. Exceptions are exergy and solar energy-related methods, which cover the widest range of resource categories. However, these methods do not link exergy consumption to changes in availability or provisioning capacity of a specific natural resource (e.g., mineral, water, land etc.). So far, there is no agreement in the scientific community on the most relevant type of future resource indicators (depletion, increased energy use or cost due to resource extraction, etc.). To address this challenge, a framework based on the concept of stock/fund/flow resources is proposed to identify, across natural resource categories, whether depletion/dissipation (of stocks and funds) or competition (for flows) is the main relevant aspect. Conclusions. An LCIA method—or a set of methods—that consistently address all natural resource categories is needed in order to avoid burden shifting from the impact associated with one resource to the impact associated with another resource. This paper is an important basis for a step forward in the direction of consistently integrating the various natural resources as an Area of Protection into LCA

HP1 proteins compact DNA into mechanically and positionally stable phase separated domains

© The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Keenen, M. M., Brown, D., Brennan, L. D., Renger, R., Khoo, H., Carlson, C. R., Huang, B., Grill, S. W., Narlikar, G. J., & Redding, S. HP1 proteins compact DNA into mechanically and positionally stable phase separated domains. Elife, 10, (2021): e64563, https://doi.org/10.7554/eLife.64563.In mammals, HP1-mediated heterochromatin forms positionally and mechanically stable genomic domains even though the component HP1 paralogs, HP1α, HP1β, and HP1γ, display rapid on-off dynamics. Here, we investigate whether phase-separation by HP1 proteins can explain these biological observations. Using bulk and single-molecule methods, we show that, within phase-separated HP1α-DNA condensates, HP1α acts as a dynamic liquid, while compacted DNA molecules are constrained in local territories. These condensates are resistant to large forces yet can be readily dissolved by HP1β. Finally, we find that differences in each HP1 paralog’s DNA compaction and phase-separation properties arise from their respective disordered regions. Our findings suggest a generalizable model for genome organization in which a pool of weakly bound proteins collectively capitalize on the polymer properties of DNA to produce self-organizing domains that are simultaneously resistant to large forces at the mesoscale and susceptible to competition at the molecular scale.MMK was supported by the Discovery Fellows Program at UCSF and NCI grants F31CA243360 and F99CA245719. RR was support from the NOMIS foundation, Rostock, Germany. BH acknowledges support though NIH R21 GM129652, R01 CA231300 and R01 GM131641. BH is also a Chan Zuckerberg Biohub Investigator. SWG was supported by the DFG (SPP 1782, GSC 97, GR 3271/2, GR 3271/3, GR 3271/4) and the European Research Council (grant 742712). GJN acknowledges support from NIH grant R35 GM127020 and NSF grant 1921794. Support to SR through the UCSF Program for Breakthrough Biomedical Research (PBBR), Sandler Foundation, and Whitman Foundation at the Marine Biological Laboratories

Angle- and polarization-resolved luminescence from suspended and hexagonal boron nitride encapsulated MoSe2 monolayers

The polarized photoluminescence from atomically thin transition metal dichalcogenides is a frequently applied tool to scrutinize optical selection rules and valley physics, yet it is known to sensibly depend on a variety of internal and external material and sample properties. In this work, we apply combined angle- and polarization-resolved spectroscopy to explore the interplay of excitonic physics and phenomena arising from the commonly utilized encapsulation procedure on the optical properties of atomically thinMoSe2.We probe monolayers prepared in both suspended and encapsulated manners.We show that the hBN encapsulation significantly enhances the linear polarization of exciton photoluminescence emission at large emission angles. This degree of linear polarization of excitons can increase up to ∼17% in the hBN encapsulated samples. As we confirm by finite-difference time-domain simulations, it can be directly connected to the optical anisotropy of the hBN layers. In comparison, the linear polarization at finite exciton momenta is significantly reduced in a suspendedMoSe2 monolayer, and becomes notable only in cryogenic conditions. This phenomenon strongly suggests that the effect is rooted in the k-dependent anisotropic exchange coupling inherent in2Dexcitons.Our results have strong implications on further studies on valley contrasting selection rules and valley coherence phenomena using standard suspended and encapsulated samples