Notes

The 4 Lethal Mistakes regarding Play acted Attitude Study.
Triptycenetribenzoquinone (BQ)3, where the three benzene rings of triptycene are replaced by 1,4-benzoquinone (BQ) rings, is known to be reduced to triptycenetrihydroquinone (HQ)3. In contrast, a molecule where both BQ and HQ moieties coexist in a triptycene framework has never been reported. In this study, triptycenemonohydroquinonedibenzoquinone ((HQ)1(BQ)2) in which one HQ unit and two BQ units coexist was generated by comproportionation between (BQ)3 and (HQ)3 and isolated by recrystallization. We obtained two types of crystals with different hydrogen-bonding structures by changing the cosolvents.Cyclodextrins are well known for their ability to form stable, highly soluble complexes with various substances, which makes them widely used as excipients in food, cosmetics, and pharmaceuticals. In this work, properties of heptakis(2,6-O-dimethyl)-β-cyclodextrin (DM-β-CD) in vacuo and in water, as well as its ability to bind the antidepressant drug mianserin (MIA) in aqueous solution, are investigated computationally. The results are shown to depend strongly on the density functional theory (DFT) applied. The most stable conformers of DM-β-CD found with the B3LYP-GD2 method differ from these indicated by M062X-GD3 and other functionals. According to the latter, two crystal structures, ZULQAY and BOYFOK03, optimized in vacuo and in water, respectively, have the lowest energy. Both the B3LYP-GD2 and M062X-GD3 results show that all tested inclusion and noninclusion complexes of MIADM-β-CD in stoichiometry 11 are stable in water. However, the structures and their energetic properties obtained with each method differ in the most stable configurations, different aromatic rings of MIA are embedded inside DM-β-CD, and the corresponding complexation energies (calculated with the 6-31++G(d,p) basis set and corrected for the basis set superposition error) are -29.6 (B3LYP-GD2) and -23.9 (M062X-GD3) kcal/mol. The NMR spectra of DM-β-CD and MIADM-β-CD are also compared.A unique prenylated bicarbazole alkaloid, clausanisumine (1), and two biogenetically related known monomer carbazole alkaloids, mukonal (2) and 3-methylcarbazole (3), were isolated from the fruits of Clausena anisum-olens. Clausanisumine (1) was an uncommon prenylated bicarbazole alkaloid, possessing an unprecedented carbon skeleton, which was composed of a simple carbazole alkaloid and a prenylated carbazole alkaloid. The chemical structure of 1 was established by a combination of comprehensive spectral methods. A plausible biosynthetic pathway of 1 was also proposed. Additionally, the potential anti-HIV activities of all isolates 1-3 in vitro were evaluated. Compound 1 exhibited remarkable anti-HIV-1 reverse transcriptase effects showing an EC50 value of 18.58 nM. The discovery of the prenylated bicarbazole alkaloid from C. anisum-olens with notable anti-HIV activity would be meaningful to discovering and developing new anti-HIV drugs.The design and preparation of molecular systems with multiple geometric and electronic configurations are the cornerstones for multifunctional materials with stimuli-responsive behaviors. We describe here the regioselective and facile synthesis of two types of overcrowded ethylene-bridged nanohoop dimers, with folded and twisted geometric structures as well as closed-shell, diradical and dication electronic structures. The strained nanohoop structures have a profound effect on the overall molecular and electronic configurations, which resulted in the destabilized diradical state. X-ray crystallographic analysis revealed the folded molecular geometry for the neutral species and twisted geometry for the dication species. The unique molecular dynamics, optical properties, and dynamic redox properties were disclosed in the solution phase by spectroscopic and electrochemical methods. Furthermore, the global Hückel and Möbius aromaticity were revealed by a combination of experimental and theoretical approaches. Our studies shed light on the design of nanohoop-incorporated multiconfigurational materials with unique topologies and functions.Chemoproteomic profiling of cysteines has emerged as a powerful method for screening the proteome-wide targets of cysteine-reactive fragments, drugs, and natural products. Herein, we report the development and an in-depth evaluation of a tetrafluoroalkyl benziodoxole (TFBX) as a cysteine-selective chemoproteomic probe. We show that this probe features numerous key improvements compared to the traditionally used cysteine-reactive probes, including a superior target occupancy, faster labeling kinetics, and broader proteomic coverage, thus enabling profiling of cysteines directly in live cells. In addition, the fluorine "signature" of probe 7 constitutes an additional advantage resulting in a more confident adduct-amino acid site assignment in mass-spectrometry-based identification workflows. We demonstrate the utility of our new probe for proteome-wide target profiling by identifying the cellular targets of (-)-myrocin G, an antiproliferative fungal natural product with a to-date unknown mechanism of action. We show that this natural product and a simplified analogue target the X-ray repair cross-complementing protein 5 (XRCC5), an ATP-dependent DNA helicase that primes DNA repair machinery for nonhomologous end joining (NHEJ) upon DNA double-strand breaks, making them the first reported inhibitors of this biomedically highly important protein. We further demonstrate that myrocins disrupt the interaction of XRCC5 with DNA leading to sensitization of cancer cells to the chemotherapeutic agent etoposide as well as UV-light-induced DNA damage. Altogether, our next-generation cysteine-reactive probe enables broader and deeper profiling of the cysteinome, rendering it a highly attractive tool for elucidation of targets of electrophilic small molecules.Myriad neuropsychiatric disorders are due to dopamine dysfunction. However, understanding these disorders is limited by our ability to measure dopamine storage and release. Fluorescent false neurotransmitters (FFNs), small-molecule dyes that co-transit through the synaptic vesicle cycle, have allowed us to image dopamine in cell culture and acute brain slice, but in vivo microscopy is constrained by the biopenetrance of light. Here, we adapt FFNs into magnetic resonance false neurotransmitters (MFNs). The design principles guiding MFNs are (1) the molecule is a valid false neurotransmitter and (2) it has a 19F-substituent near a pH-sensing functional group, which (3) has pKa close to 6 so that the probe within vesicles is protonated. We demonstrate that MFN103 meets these criteria. While a magnetic resonance spectroscopy (MRS) signal was too low for measurement in vivo with the current technology, in principle, MFNs can quantify neurotransmitters within and without synaptic vesicles, which may underlie noninvasive in vivo analysis of dopamine neurotransmission.The integration of metallic oxide and metal-organic frameworks has attracted considerable attention as obtained composite materials because they show synergistic effects in applications of catalysis and sensing. Herein, we developed the hybrid MgO and HKUST-1 for efficient capture, catalysis, and cyclic cataluminescence (CCTL) detection of esters all-in-one to rapidly identify scented products. The multifunctional MgO/HKUST-1 composite with high CCTL activity was synthesized and characterized. The multifunctional MgO/HKUST-1 composite acts as an enrichment material for ester capture and serves as a catalyst, assisting the analyte to trigger multistage signals. The multistage signals of ester-containing scented products also satisfy the exponential decay equation with a certain τ-value. The τ-values obtained by the CCTL system were applied to identify the brands of essential oils. The working temperature served as the sensor element to obtain various τ-values. The τ-values constituted a digital code to label the different brands of cigarettes with the same aroma type. The multistage signals could be used to distinguish the origin regions of essential oils and tobacco. This work combines the CCTL strategy with the sample pretreatment, opening up a new direction to develop CCL and providing a new platform to rapidly identify ester-containing scented products.OX1 receptor antagonists are of interest to treat, for example, substance abuse disorders, personality disorders, eating disorders, or anxiety-related disorders. However, known dual OX1/OX2 receptor antagonists are not suitable due to their sleep-inducing effects; therefore, we were interested in identifying a highly OX1 selective antagonist with a sufficient window to OX2-mediated effects. Herein, we describe the design of highly selective OX1 receptor antagonists driven by the X-ray structure of OX1 with suvorexant, a dual OX1/OX2 receptor antagonist. Moderately selective OX1 antagonists comprising a [2.2.1]-bicyclic scaffold served as our starting point. Based on our binding mode hypothesis, we postulated which part of the scaffold points toward one of the regions where the two binding pockets differ. Structural changes in this part resulted in a modified core with higher inherent selectivity compared to the [2.2.1]-bicyclic template. The structure-based design, synthesis, and hit-to-lead evaluation of this novel OX1 receptor-selective scaffold are discussed herein.Smart textiles with tunable luminescence have received special attention due to their great potential in various advanced photonic applications. Particularly, the development of one-dimensional, on-demand, responsive fluorescence fibers with excellent adaptability is of great significance. Herein, we propose electro-thermochromic fluorescence fibers regulated by a self-crystallinity phase change; that is, their tunable luminescence properties are derived from the reversible conversion of the dispersion state and fluorescence emission of fluorophore molecules during the crystallization/melting processes of phase-change materials. First results obtained with an alginate wet-spinning system demonstrate that the self-crystallinity phase change can produce polymeric fibers with thermochromic fluorescence behavior, which are prepared using microemulsion particles containing a phase-change fatty acid and coumarin fluorescent dyes. These thermochromic fluorescence fibers possess a fast response speed, high emission contrast, and good reversibility (>100 cycles). Particularly, the thermochromic fluorescent fibers can gain an electrotriggered capability by means of electric heating materials, and their great potential in precision operation applications is demonstrated. It is easy to adjust the switching point of the electro-thermochromic fluorescence fibers, highlighting their potential use in a diverse range of applications, the designs of which can be personalized. This work offers a simple yet versatile strategy for constructing electro-thermochromic fluorescence fibers for advanced smart textiles.A tripod molecule incorporating a C60 photocatalyst into a rigid scaffold with disulfide legs was designed and synthesized for the stable and robust attachment of C60 onto an Au-coated atomic force microscope (AFM) tip. The "tripod-C60" was immobilized onto the tip by forming S-Au bonds in the desired orientation and a dispersed manner, rendering it suitable for the oxidation and scission of single molecules on a countersurface, thereby functioning as "molecular shears". A DNA origami with a well-defined structure was chosen as the substrate for the tip-induced oxidation. The gold-coated, C60-functionalized AFM tip was used for both AFM imaging and oxidation of DNA origami upon visible-light irradiation. The localized and temporally controlled oxidative damage of DNA origami was successfully performed at the single-molecule level via singlet-oxygen (1O2) generation from the immobilized C60 on the AFM tip. This oxidative damage to DNA origami can be carried out under ambient conditions in a fluid cell at room temperature, rendering it well-suited for the manipulation of a variety of species on surfaces via a spatially and temporally controlled oxidation reaction triggered by 1O2 locally generated from the immobilized C60 on the AFM tip.
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