Ballardjones8091

The construction of two Boolean logic gates (OR, and AND) was realized.A one-pot synthetic route has been developed for the assembly of peptide Mn(i)-carbonyl bioconjugates. It allows the installation of a variety of chelating agents at the late stage, and after just one purification step the TAT-MnCO complexes can be obtained. The resulting bioconjugates showed different and tunable CO releasing kinetics upon visible light activation.The modulation of SK3 ion channels can be efficiently and selectively achieved by using the amphiphilic compound Ohmline (a glyco-glycero-ether-lipid). We report herein a series of Ohmline analogues featuring the replacement of one ether function by a thioether function located at the same position or shifted close to its initial position. The variation of the lipid chain length and the preparation of two analogues featuring either one sulfoxide or one sulfone moiety complete this series. Patch clamp measurements indicate that the presence of the thioether function (compounds 7 and 17a) produces strong activators of SK3 channels, whereas the introduction of a sulfoxide or a sulfone function at the same place produces amphiphiles devoid of an effect on SK3 channels. Compounds 7 and 17a are the first amphiphilic compounds featuring strong activation of SK3 channels (close to 200% activation). The cytosolic calcium concentration determined from fluorescence at 3 different times for compound 7b (13 min, 1 h, 24 h) revealed that the effect is different suggesting that the compound could be metabolized over time. This compound could be used as a strong SK3 activator for a short time. The capacity of 7b to activate SK3 was then used to induce vasorelaxation via an endothelium-derived hyperpolarization (EDH) pathway. For the first time, we report that an amphiphilic compound can affect the endothelium dependent vasorelaxation.Density functional theory (DFT) calculations (M06-2X) have been employed to disclose the mechanisms and regio- and stereo-selectivities of the N-heterocyclic carbene (NHC)-catalyzed reaction of 2-benzothiazolimines and α-chloroaldehydes. The preferred mechanism is initiated by the nucleophilic attack of NHC on α-chloroaldehyde (first step), followed by 1,2-proton transfer which was assisted by the Brønsted acid DABCO·H+ to generate the Breslow intermediate (second step). The cleavage of the C-Cl bond (third step) and deprotonation (fourth step) form the enolate intermediate. This further reacts with 2-benzothiazolimine which leads to the formation of a new C-C bond (fifth step). Subsequent cyclization takes place via the formation of a new C-N bond (sixth step). Catalyst regeneration completes the whole catalytic cycle and affords the final product (seventh step). The DFT results indicate that the fifth step determines the stereochemistry of the reaction and leads to benzothiazolopyrimidinone with the SS configuration, which agrees well with experimental observations. Intramolecular cyclization is found to be the regioselectivity-determining step, for which the [4+2] annulation pathway is more preferred than that via [2+2] annulation, which again agrees well with experimental observations. Based on the mechanism proposed, the origins of regio- and stereoselectivities have also been investigated by performing distortion/interaction, natural bond orbital (NBO) and non-covalent interaction (NCI) analyses. this website The mechanistic insights gained in this work should be helpful in the rational design of potential catalysts for analogous reactions.The spatial arrangement of heterostructures based on two-dimensional layered materials is important in controlling their electronic and optoelectronic properties. In this contribution, by controlling the reaction kinetics and thus the nucleation and growth sequence of p-type SnS and metallic NbS2, controllable preparation of both SnS@NbS2 core@shell and SnS/NbS2 lateral heterostructures was realized. The SnS@NbS2 core@shell heterostructures were further applied in photodetectors, and interestingly, a negative photoresponse was observed due to the Seebeck effect exerted on the NbS2 shell. Compared with the pure metallic NbS2, the SnS@NbS2 core@shell heterostructures showed a 15 times increased signal-to-noise ratio and much improved photocurrent stability, largely due to the charge and heat transfer between the SnS core and NbS2 shell.Lithium ion batteries (LIBs) have become indispensable in daily life. Here, we fabricated a broad range of polymer semiconductor films as thin as 2 nm via a standard spin-coating method, and utilized the resulting organic transistors for the detection of LIB electrolytes, which can give an early warning signal before LIB failure.Non-apoptotic cell death such as ferroptosis and pyroptosis has shed new light on cancer treatment, whereas combinational therapy using both these mechanisms has not yet been fully explored. link2 Herein, a dual-inductive nano-system to realize ferroptosis/pyroptosis mediated anti-cancer effects is presented. The nanodrug (Tf-LipoMof@PL) is constructed with a piperlongumine (PL) loaded metal-organic framework (MOF) coated with transferrin decorated pH sensitive lipid layer. Intracellular iron was enriched with an iron-containing MOF, whose endocytosis can be further facilitated by transferrin decorated on the lipid layer, which provides a prerequisite for the occurrence of ferroptosis and pyroptosis. Piperlongumine as the ferroptosis inducer can strengthen the ferroptotic cell death, and provide H2O2 for the dual induction system to increase ROS generation through Fenton reaction. On the basis of validation of both ferroptosis and pyroptosis, the dual-inductive nanodrug demonstrated ideal anticancer effects in the xenograft mice model, which proved that the ferroptosis/pyroptosis dual-inductive nanoplatform could be an effective and promising anticancer modality.A novel method for a mild copper-catalyzed selective monoalkylation of active methylene compounds with various alkylsilyl peroxides has been developed. The reaction has a broad substrate scope and our mechanistic studies suggest the participation of radical species in this alkylation reaction.We demonstrate polymeric piezocapacitive pressure sensors based on a novel composite dielectric film of poly(dimethylsiloxane) elastomeric silicone and zinc oxide tetrapod. With an appropriate loading of zinc oxide tetrapods, composite piezocapacitive pressure sensors show a 75-fold enhancement of pressure sensitivity over pristine devices, achieving a marked value as high as 2.55 kPa-1. The limit of detection was estimated to be about 10 mg, corresponding to a subtle stimulus of only 1.0 Pa. Besides, versatile functionalities such as detection of finger bending/straightening, calligraphy writing, and air flow blowing have been investigated. It is expected that the proposed piezocapacitive pressure sensors incorporating stress-sensitive additives of zinc oxide nanostructures may provide a promising means for potential applications in ultrasensitive wearable, healthcare systems and human-machine interfaces.The use of aliphatic amines as alkylating reagents in organic synthesis via C-N bond activation remains underdeveloped. We herein describe a novel ruthenium-catalysed and directing-group assisted protocol for the synthesis of meta-alkylated arenes via dual C-H and C-N activation. link3 Bench-stable and easily handled redox-active Katritzky pyridinium salts derived from abundant amines and amino acid species were used as alkyl radical precursors. This catalytic reaction could accommodate a broad range of functional groups and provide access to various meta-alkylated products.This review describes recent studies on coupled plasmonic systems for controlling plasmon dynamics and molecular detection using spectral modulations. The plasmon dephasing time can be controlled by weak and strong coupling regimes between the plasmonic nanostructures or localized surface plasmon resonances (LSPRs) and the other optical modes such as microcavities. The modal coupling induces near-field enhancement by extending the plasmon dephasing time to increase the near-field enhancement at certain wavelengths resulting in the enhancement of molecular detection. On the other hand, the interaction between LSPR and molecular excited or vibrational states also modulates the resonance spectrum, which can also be used for detecting a small number of molecules with a subtle change in the spectrum. The spectral modulation is induced by weak and strong couplings between LSPRs and the electronic or vibrational states of molecules, and this method is sensitive enough to measure a single molecule.Protein O-GlcNAcylation refers to the covalent binding of a single N-acetylglucosamine (GlcNAc) to the serine or threonine residue. This modification primarily occurs on proteins in the nucleus and the cytosol, and plays critical roles in many cellular events, including regulation of gene expression and signal transduction. Aberrant protein O-GlcNAcylation is directly related to human diseases such as cancers, diabetes and neurodegenerative diseases. In the past decades, considerable progress has been made for global and site-specific analysis of O-GlcNAcylation in complex biological samples using mass spectrometry (MS)-based proteomics. In this review, we summarized previous efforts on comprehensive investigation of protein O-GlcNAcylation by MS. Specifically, the review is focused on methods for enriching and site-specifically mapping O-GlcNAcylated peptides, and applications for quantifying protein O-GlcNAcylation in different biological systems. As O-GlcNAcylation is an important protein modification for cell survival, effective methods are essential for advancing our understanding of glycoprotein functions and cellular events.The reaction of a chlorosilylene, supported by an iminophosphonamide ligand, with KN(SiMe3)2 resulted in the formation of a silaimine instead of the expected aminosilylene. However, this silaimine exists in equilibrium with the corresponding aminosilylene, which was experimentally demonstrated using variable-temperature NMR spectroscopy and a trapping reaction with elemental selenium to give a silaselenourea.Recently, it has been proven that the biaxial strain (ε), electric field (E) and interlayer distance (d) can effectively modulate the electronic structure and magnetic properties of two-dimensional (2D) van der Waals (vdW) heterostructures, which have potential applications in spintronic devices. Here, the electronic structure and magnetic properties of 2D g-C3N4/Li-adsorbed Cr2Ge2Te6 vdW heterostructures are investigated using first-principles calculations. Their lattice structures are seriously affected by adsorption combination. With external stimulation, the band gap of the heterostructures changes. The heterostructures are metallic at ε = -6% and -4%, and others are n-type semiconductors, where the band gap is 23 meV at ε = 6%. In addition, the magnetic moments of g-C3N4 in the adsorption systems are in the range from 0.029 to 0.226 μB. The vdW heterostructures show in-plane magnetic anisotropy (IMA) at ε = -6%, -2% and 6% and perpendicular magnetic anisotropy (PMA) at ε = -4%, 0, 2% and 4%. On applying an electric field and changing the interlayer distance, the vdW heterostructures show PMA.