210 research outputs found
Sulfur-doped Nanographenes Containing Multiple Subhelicenes
In this work, we describe the synthesis and characterization of three novel sulfur-doped nanographenes (NGs) (1â3) containing multiple subhelicenes, including carbo[4]helicenes, thieno[4]helicenes, carbo[5]helicenes, and thieno[5]helicenes. Density functional theory calculations reveal that the helicene substructures in 1â3 possess dihedral angles from 15° to 34°. The optical energy gaps of 1â3 are estimated to be 2.67, 2.45, and 2.30 eV, respectively. These three sulfur-doped NGs show enlarged energy gaps compared to those of their pristine carbon analogues
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Synthesis and Self-Assembly Behavior of Double Ullazine-Based Polycyclic Aromatic Hydrocarbons
Polycyclic aromatic azomethine ylides (PAMY, 1) are versatile building blocks for the bottom-up synthesis of nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Although the chemistry of PAMY was already established few years ago, the cycloaddition of a double PAMY building block has not been reported so far. In this work, we demonstrate the first cycloaddition of a PAMY-dimer (6), which opens the access to three different alkyl ester-substituted N-PAHs with a laterally extended double ullazine scaffold (DU-1, DU-2 and DU-3). Interestingly, the cyclic voltammetry of DU-1-3 exhibited three reversible oxidation waves, which confirmed the electron-rich nature of the double ullazine scaffold. Furthermore, in-situ spectroelectrochemistry study of ethylhexyl ester-substituted DU-3 revealed the formation of different cationic species with new absorption bands up to 1689 nm. Additionally, the influence of the attached substituents on the film formation and supramolecular organization in the thin films were investigated by polarized optical microscopy and grazing incidence wide-angle X-ray scattering
TMEM110 regulates the maintenance and remodeling of mammalian ERâplasma membrane junctions competent for STIMâORAI signaling
The stromal interaction molecule (STIM)âORAI calcium release-activated calcium modulator (ORAI) pathway controls store-dependent calcium entry, a major mechanism of physiological calcium signaling in mammalian cells. The core elements of the pathway are the regulatory protein STIM1, located in the endoplasmic reticulum (ER) membrane, the calcium channel ORAI1 in the plasma membrane, and sites of close contact between the ER and the plasma membrane that permit the two proteins to interact. Research on calcium signaling has centered on STIM1, ORAI1, and a few proteins that directly modulate STIMâORAI function. However, little is known about proteins that organize ERâplasma membrane junctions for STIMâORAI-dependent calcium signaling. Here, we report that an ER-resident membrane protein identified in a previous genome-wide RNAi screen, transmembrane protein 110 (TMEM110), regulates the long-term maintenance of ERâplasma membrane junctions and the short-term physiological remodeling of the junctions during store-dependent calcium signaling
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Helical Nanographenes Containing an Azulene Unit : Synthesis, Crystal Structures, and Properties
Three unprecedented helical nanographenes (1, 2, and 3) containing an azulene unit are synthesized. The resultant helical structures are unambiguously confirmed by X-ray crystallographic analysis. The embedded azulene unit in 2 possesses a record-high twisting degree (16.1°) as a result of the contiguous steric repulsion at the helical inner rim. Structural analysis in combination with theoretical calculations reveals that these helical nanographenes manifest a global aromatic structure, while the inner azulene unit exhibits weak antiaromatic character. Furthermore, UV/Vis-spectral measurements reveal that superhelicenes 2 and 3 possess narrow energy gaps (2: 1.88 eV; 3: 2.03 eV), as corroborated by cyclic voltammetry and supported by density functional theory (DFT) calculations. The stable oxidized and reduced states of 2 and 3 are characterized by in-situ EPR/VisâNIR spectroelectrochemistry. Our study provides a novel synthetic strategy for helical nanographenes containing azulene units as well as their associated structures and physical properties. © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA
Optogenetic Control of Non-Apoptotic Cell Death
Herein, a set of optogenetic tools (designated LiPOP) that enable photoswitchable necroptosis and pyroptosis in live cells with varying kinetics, is introduced. The LiPOP tools allow reconstruction of the key molecular steps involved in these two non-apoptotic cell death pathways by harnessing the power of light. Further, the use of LiPOPs coupled with upconversion nanoparticles or bioluminescence is demonstrated to achieve wireless optogenetic or chemo-optogenetic killing of cancer cells in multiple mouse tumor models. LiPOPs can trigger necroptotic and pyroptotic cell death in cultured prokaryotic or eukaryotic cells and in living animals, and set the stage for studying the role of non-apoptotic cell death pathways during microbial infection and anti-tumor immunity
Near-infrared photoactivatable control of Ca signaling and optogenetic immunomodulation
The application of current channelrhodopsin-based optogenetic tools is limited by the lack of strict ion selectivity and the inability to extend the spectra sensitivity into the near-infrared (NIR) tissue transmissible range. Here we present an NIR-stimulable optogenetic platform (termed Opto-CRAC ) that selectively and remotely controls Ca2+ oscillations and Ca2+-responsive gene expression to regulate the function of non-excitable cells, including T lymphocytes, macrophages and dendritic cells. When coupled to upconversion nanoparticles, the optogenetic operation window is shifted from the visible range to NIR wavelengths to enable wireless photoactivation of Ca2+-dependent signaling and optogenetic modulation of immunoinflammatory responses. In a mouse model of melanoma by using ovalbumin as surrogate tumor antigen, Opto-CRAC has been shown to act as a genetically-encoded photoactivatable adjuvant to improve antigen-specific immune responses to specifically destruct tumor cells. Our study represents a solid step forward towards the goal of achieving remote control of Ca2+-modulated activities with tailored function
Distribution of transparent exopolymer particles and their response to phytoplankton community structure changes in the Amundsen Sea, Antarctica
To understand the response of transparent exopolymer particles (TEP) to the changes in phytoplankton communities caused by melting sea ice, we collected samples from the polynya and open ocean affected by the Antarctic circumpolar current in the Amundsen Sea. TEP, pigments, and other environmental factors were analyzed. The results showed that high TEP content was mainly found in the polynya, and was higher in the surface layer than in the deep layer. The main factor that affected TEP distribution was the phytoplankton community. In the polynya area, the phytoplankton were dominated by low-iron Haptophyta. In the Antarctic circumpolar current region affected by ice-melting water, the dominant species was diatom type II. Our results revealed that low-iron Haptophyta may be the main contributors to TEP content
Bottom-up Solution Synthesis of Graphene Nanoribbons with Precisely Engineered Nanopores
The incorporation of nanopores into graphene nanostructures has been demonstrated as an efficient tool in tuning their band gaps and electronic structures. However, precisely embedding the uniform nanopores into graphene nanoribbons (GNRs) at the atomic level remains underdeveloped especially for in-solution synthesis due to the lack of efficient synthetic strategies. Herein we report the first case of solution-synthesized porous GNR (pGNR) with a fully conjugated backbone via the efficient Scholl reaction of tailor-made polyphenylene precursor (P1) bearing pre-installed hexagonal nanopores. The resultant pGNR features periodic subnanometer pores with a uniform diameter of 0.6 nm and an adjacent-pores-distance of 1.7 nm. To solidify our design strategy, two porous model compounds (1 a, 1 b) containing the same pore size as the shortcuts of pGNR, are successfully synthesized. The chemical structure and photophysical properties of pGNR are investigated by various spectroscopic analyses. Notably, the embedded periodic nanopores largely reduce the Ï-conjugation degree and alleviate the inter-ribbon ÏâÏ interactions, compared to the nonporous GNRs with similar widths, affording pGNR with a notably enlarged band gap and enhanced liquid-phase processability
Ultrafast control of vortex microlasers
The development of classical and quantum information-processing technology calls for on-chip integrated sources of structured light. Although integrated vortex microlasers have been previously demonstrated, they remain static and possess relatively high lasing thresholds, making them unsuitable for high-speed optical communication and computing. We introduce perovskite-based vortex microlasers and demonstrate their application to ultrafast all-optical switching at room temperature. By exploiting both mode symmetry and far-field properties, we reveal that the vortex beam lasing can be switched to linearly polarized beam lasing, or vice versa, with switching times of 1 to 1.5 picoseconds and energy consumption that is orders of magnitude lower than in previously demonstrated all-optical switching. Our results provide an approach that breaks the long-standing trade-off between low energy consumption and high-speed nanophotonics, introducing vortex microlasers that are switchable at terahertz frequencies.This research was supported by the
National Key Research and Development Program of China (grant
no. SQ2018YFB220027), the Shenzhen Fundamental Research
Fund (grant no. JCYJ20180507184613841), the Australian
Research Council (grant no. DP200101168), and the National
Science Foundation (grant no. PHY-1847240). The authors also
acknowledge support from the Shenzhen Engineering Laboratory
on Organic-Inorganic Perovskite Device
Near-infrared photoactivatable control of Ca2+ signaling and optogenetic immunomodulation
The application of current channelrhodopsin-based optogenetic tools is limited by the lack of strict ion selectivity and the inability to extend the spectra sensitivity into the near-infrared (NIR) tissue transmissible range. Here we present an NIR-stimulable optogenetic platform (termed 'Opto-CRAC') that selectively and remotely controls Ca(2+) oscillations and Ca(2+)-responsive gene expression to regulate the function of non-excitable cells, including T lymphocytes, macrophages and dendritic cells. When coupled to upconversion nanoparticles, the optogenetic operation window is shifted from the visible range to NIR wavelengths to enable wireless photoactivation of Ca(2+)-dependent signaling and optogenetic modulation of immunoinflammatory responses. In a mouse model of melanoma by using ovalbumin as surrogate tumor antigen, Opto-CRAC has been shown to act as a genetically-encoded 'photoactivatable adjuvant' to improve antigen-specific immune responses to specifically destruct tumor cells. Our study represents a solid step forward towards the goal of achieving remote and wireless control of Ca(2+)-modulated activities with tailored function. DOI: http://dx.doi.org/10.7554/eLife.10024.00
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