Engbergstanton8944

Spins in molecules are particularly attractive targets for next-generation quantum technologies, enabling chemically programmable qubits and potential for scale-up via self-assembly. Here we report the observation of one of the largest hyperfine interactions for a molecular system, Aiso = 3,467 ± 50 MHz, as well as a very large associated clock transition. This is achieved through chemical control of the degree of s-orbital mixing into the spin-bearing d orbital associated with a series of spin-½ La(II) and Lu(II) complexes. Increased s-orbital character reduces spin-orbit coupling and enhances the electron-nuclear Fermi contact interaction. Both outcomes are advantageous for quantum applications. The former reduces spin-lattice relaxation, and the latter maximizes the hyperfine interaction, which, in turn, generates a 9-GHz clock transition, leading to an increase in phase memory time from 1.0 ± 0.4 to 12 ± 1 μs for one of the Lu(II) complexes. These findings suggest strategies for the development of molecular quantum technologies, akin to trapped ion systems.Three new lipopeptaibols, halovirs I-K (1-3), were isolated from the solid culture of the phytopathogenic fungus Paramyrothecium roridum NRRL 2183. Their planar structures, which consist of a hexapeptide backbone and acyl substitutions at the N- and C-termini, were elucidated by comprehensive analysis of the 1D and 2D NMR spectroscopic data along with the detailed interpretation of the MS/MS fragmentation pattern. Absolute configurations of the amino acid/1,2-amino alcohol residues were determined using the advanced Marfey's method. Bioinformatics analysis of the genome assembly of P. roridum NRRL 2183 revealed a gene cluster that is likely responsible for the biosynthesis of halovirs I-K. Analysis of the module and domain organization of the putative halovir synthetase PrHalA indicated that the assembly of 1-3 proceeds in an unconventional nonlinear fashion. 1 and 2 exhibited potent antibacterial activity against both antibiotic-sensitive and multidrug-resistant Gram-positive pathogens. These lipopeptaibols also displayed significant cytotoxicity toward human lung carcinoma A549, human breast carcinoma MCF-7, and human cervical carcinoma HeLa cells with IC50 values ranging from 1.3 to 3.3 μM.A new cytotoxic pentacyclic alkaloid, citrinadin C (1), together with four known compounds (2-5), were isolated from deep-sea-derived fungus Penicillium citrinum. The structure of new compound 1 was elucidated by extensive 1D and 2D NMR and Mass spectroscopic data, and its absolute configuration was determined by CD spectrum. All the compounds were evaluated for their cytotoxic and antibacterial activities. Compound 1 showed cytotoxic activities against human liver cancer cell line MHCC97H, with IC50 value of 16.7 μM. Compound 4 displayed significant antibacterial activity against phytopathogen Xanthomonas campestris, with MIC value of 25 μM.Triclabendazole (TBD) has been widely used in the treatment of helminthic infection. The anti-biofilm activity and antibacterial mechanism of TBD against Staphylococcus aureus were not known. Here, the anti-biofilm activity of TBD against clinical S. aureus isolates from China was systematically evaluated. Under TBD pressure, TBD-induced tolerant S. aureus with elevated TBD minimum inhibitory concentration (MIC) was selected in vitro and the genetic mutations between the parental isolates and TBD-induced tolerant derivatives were determined by whole-genome sequencing. TBD could significantly inhibit biofilm formation at sub-inhibitory concentration and disperse mature biofilm of clinical S. aureus isolates. In addition, TBD displayed bactericidal activity against the bacterial cells embedded in the biofilm and showed anti-persisters activity. Proteomic analysis showed that KEGG pathways of ABC transporters and beta-lactam resistance were significantly changed after TBD exposure. Moreover, SAUSA300_RS08395 (molecular chaperone DnaK), SAUSA300_RS11200 (sensor histidine kinase KdpD), SAUSA300_RS06325 (DNA translocase FtsK) were identified as candidate targets of TBD in S. aureus. Overexpression experiments further demonstrated that the elevated transcriptional level of DnaK resulted in S. aureus growth delay after exposure to a sub-MIC concentration of 1/2× MIC TBD. In conclusion, TBD exhibits antibacterial and anti-biofilm activity against S. aureus possibly by targeting the DnaK chaperone system.Pyroptosis, an inflammatory form of lytic cell death, is a type of cell death mediated by the gasdermin (GSDM) protein family. Upon recognizing exogenous or endogenous signals, cells undergo inflammasome assembly, GSDM cleavage, the release of proinflammatory cytokines and other cellular contents, eventually leading to inflammatory cell death. In this review, we discuss the roles of the GSDM family for anti-cancer functions and various antitumor drugs that could activate the pyroptosis pathways.Semiconductor moiré superlattices represent a rapidly developing area of engineered photonic materials and a new platform to explore correlated electron states and quantum simulation. In this Review, we briefly introduce early experiments that identified new exciton resonances in transition metal dichalcogenide heterobilayers and discuss several topics including two types of transition metal dichalcogenide moiré superlattice, new optical selection rules, early evidence of moiré excitons, and how the resonant energy, dynamics and diffusion properties of moiré excitons can be controlled via the twist angle. To interpret optical spectra, it is important to measure the energy modulation within a moiré supercell. In this context, we describe a few scanning tunnelling microscopy experiments that measure the moiré potential landscape directly. Finally, we review a few recent experiments that applied excitonic optical spectroscopy to probe correlated electron phenomena in transition metal dichalcogenide moiré superlattices.Parametric nonlinear optical processes are at the heart of nonlinear optics underpinning the central role in the generation of entangled photons as well as the realization of coherent optical sources. Exciton-polaritons are capable to sustain parametric scattering at extremely low threshold, offering a readily accessible platform to study bosonic fluids. Recently, two-dimensional transition-metal dichalcogenides (TMDs) have attracted great attention in strong light-matter interactions due to robust excitonic transitions and unique spin-valley degrees of freedom. However, further progress is hindered by the lack of realizations of strong nonlinear effects in TMD polaritons. Here, we demonstrate a realization of nonlinear optical parametric polaritons in a WS2 monolayer microcavity pumped at the inflection point and triggered in the ground state. We observed the formation of a phase-matched idler state and nonlinear amplification that preserves the valley population and survives up to room temperature. Our results open a new door towards the realization of the future for all-optical valley polariton nonlinear devices.Optoelectronic effects differentiating absorption of right and left circularly polarized photons in thin films of chiral materials are typically prohibitively small for their direct photocurrent observation. Chiral metasurfaces increase the electronic sensitivity to circular polarization, but their out-of-plane architecture entails manufacturing and performance trade-offs. Here, we show that nanoporous thin films of chiral nanoparticles enable high sensitivity to circular polarization due to light-induced polarization-dependent ion accumulation at nanoparticle interfaces. Self-assembled multilayers of gold nanoparticles modified with L-phenylalanine generate a photocurrent under right-handed circularly polarized light as high as 2.41 times higher than under left-handed circularly polarized light. The strong plasmonic coupling between the multiple nanoparticles producing planar chiroplasmonic modes facilitates the ejection of electrons, whose entrapment at the membrane-electrolyte interface is promoted by a thick layer of enantiopure phenylalanine. Demonstrated detection of light ellipticity with equal sensitivity at all incident angles mimics phenomenological aspects of polarization vision in marine animals. The simplicity of self-assembly and sensitivity of polarization detection found in optoionic membranes opens the door to a family of miniaturized fluidic devices for chiral photonics.Functional studies of the RNA N6-methyladenosine (m6A) modification have been limited by an inability to map individual m6A-modified sites in whole transcriptomes. To enable such studies, here, we introduce m6A-selective allyl chemical labeling and sequencing (m6A-SAC-seq), a method for quantitative, whole-transcriptome mapping of m6A at single-nucleotide resolution. The method requires only ~30 ng of poly(A) or rRNA-depleted RNA. We mapped m6A modification stoichiometries in RNA from cell lines and during in vitro monocytopoiesis from human hematopoietic stem and progenitor cells (HSPCs). We identified numerous cell-state-specific m6A sites whose methylation status was highly dynamic during cell differentiation. We observed changes of m6A stoichiometry as well as expression levels of transcripts encoding or regulated by key transcriptional factors (TFs) critical for HSPC differentiation. m6A-SAC-seq is a quantitative method to dissect the dynamics and functional roles of m6A sites in diverse biological processes using limited input RNA.Polyploidy and life-strategy transitions between annuality and perenniality often occur in flowering plants. However, the evolutionary propensities of polyploids and the genetic bases of such transitions remain elusive. We assembled chromosome-level genomes of representative perennial species across the genus Glycine including five diploids and a young allopolyploid, and constructed a Glycine super-pangenome framework by integrating 26 annual soybean genomes. These perennial diploids exhibit greater genome stability and possess fewer centromere repeats than the annuals. Biased subgenomic fractionation occurred in the allopolyploid, primarily by accumulation of small deletions in gene clusters through illegitimate recombination, which was associated with pre-existing local subgenomic differentiation. Two genes annotated to modulate vegetative-reproductive phase transition and lateral shoot outgrowth were postulated as candidates underlying the perenniality-annuality transition. Our study provides insights into polyploid genome evolution and lays a foundation for unleashing genetic potential from the perennial gene pool for soybean improvement.Colorectal cancer remains a significant cause of morbidity and mortality, even despite curative treatment. A significant proportion of patients present emergently and have poorer outcomes compared to elective presentations, independent of TNM stage. In this systematic review and meta-analysis, differences between elective/emergency presentations of colorectal cancer were examined to determine which factors were associated with emergency presentation. A literature search was carried out from 1990 to 2018 comparing elective and emergency presentations of colon and/or rectal cancer. All reported clinicopathological variables were extracted from identified studies. Variables were analysed through either systematic review or, if appropriate, meta-analysis. This study identified multiple differences between elective and emergency presentations of colorectal cancer. DZD9008 cost On meta-analysis, emergency presentations were associated with more advanced tumour stage, both overall (OR 2.05) and T/N/M/ subclassification (OR 2.56/1.