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Stereoselective syntheses of terpenoids in a more efficient manner have been a long-term pursuit for synthetic chemists. Herein we describe the two-step, enantiospecific and protecting-group-free synthesis of (+)-schisanwilsonene A from a carotane compound, which was produced in E. coli. We also completed the first enantiomeric synthesis of (+)-tormesol in five steps. The two-stage strategy offers a step- and redox-economical approach to prepare terpene natural products and their analogues.Upconversion nanoparticles have recently received increasing attention due to their outstanding performance in temperature sensing at the nanoscale. Although much effort has been devoted to improve their thermal sensitivity, there is no efficient way for achieving significant enhancement. Here, we show that lattice self-adaptation can unlock a new route for remarkably enhancing the thermal sensitivity of upconversion nanoparticles. The thermally sensitive fluorescence intensity ratio (FIR) of the dopant Er3+ is used for indicating the temperature variation, while a heterojunction of NaGdF4/NaYF4 is prepared as host material to produce a lattice distortion at the interface which is also sensitive to temperature. With the increase of temperature, the FIR of the transitions 2H11/2/4S3/2 → 4I15/2 increases, accompanied by the self-adapted decrease of interface lattice distortion that leads to the additional increase in FIR. Using core/shell upconversion nanoparticles with lattice self-adaptation, we achieve an enhanced thermal sensitivity three times higher than core-only nanoparticles.Resistance in superconductors arises from the motion of vortices driven by flowing supercurrents or external electromagnetic fields and may be strongly affected by thermal or quantum fluctuations. The common expectation is that as the temperature is lowered, vortex motion is suppressed, leading to a decreased resistance. We show experimentally that in clean-limit atomically thin 2H-NbSe2 the resistance below the superconducting transition temperature may be nonmonotonic, passing through a minimum before increasing again as the temperature is decreased further. The effect is most pronounced in monolayer devices and cannot be understood in terms of known mechanisms. buy Cyclopamine We propose a qualitative two-fluid vortex model in which thermal fluctuations of pinned vortices control the mobility of the free vortices. The findings provide a new perspective on fundamental questions of vortex mobility and dissipation in superconductors.Total synthesis of the Rhododendron meroterpenoids rubiginosins A and G, which both contain unusual 6-6-6-4 ring systems, has been achieved using a bioinspired cascade approach. Stepwise synthesis of these natural products, and the related 6-6-5-4 meroterpenoids fastinoid B and rhodonoid B, from naturally occurring chromene precursors is also reported.We present and thoroughly characterize a large collection of 3,4-dihydropyrimidin-2(1H)-ones as A2BAR antagonists, an emerging strategy in cancer (immuno) therapy. Most compounds selectively bind A2BAR, with a number of potent and selective antagonists further confirmed by functional cyclic adenosine monophosphate experiments. The series was analyzed with one of the most exhaustive free energy perturbation studies on a GPCR, obtaining an accurate model of the structure-activity relationship of this chemotype. The stereospecific binding modeled for this scaffold was confirmed by resolving the two most potent ligands [(±)-47, and (±)-38Ki = 10.20 and 23.6 nM, respectively] into their two enantiomers, isolating the affinity on the corresponding (S)-eutomers (Ki = 6.30 and 11.10 nM, respectively). The assessment of the effect in representative cytochromes (CYP3A4 and CYP2D6) demonstrated insignificant inhibitory activity, while in vitro experiments in three prostate cancer cells demonstrated that this pair of compounds exhibits a pronounced antimetastatic effect.An efficient asymmetric halogenation of cyclic diaryliodonium salts is demonstrated, which gives access to a wide range of axially chiral 2,2'-dihalobiaryls in good to excellent yields and with excellent enantioselectivities. The use of CuX with chiral bisoxazoline ligand and tetrabutylammonium halides in the unique solvent of hexafluoroisopropanol (HFIP) led to the best results in the process. The axially chiral 2,2'-dihalobiaryls can be transformed into a number of enantiopure chiral ligands that could be potentially useful in asymmetric catalysis.Owing to the tendency to form the glass state in growing crystals in the ternary tin(II) borate system, hitherto, very few single crystals in ternary tin(II) borate were reported. In this paper, a single crystal of Sn3B8O15 was obtained via a high temperature solution method in a closed system. The structure features a flexible fundamental building block [B8O18]12- constructed by one [BO3]3- unit and one [B7O16]11- group that contains three hexatomic rings, which further connect to compose a two-dimensional 2∞[B8O15] layer structure. The connection mode and flexibility of the three hexatomic B-O rings were analyzed, verifying the structural diversity of the B-O configuration. Moreover, the synthesis, crystal structure, and various characterizations were comprehensively presented. Also, theoretical calculations were employed to discuss structure-property relationships, and we use the real-space atom-cutting techniques to explain the origin of the birefringence of Sn3B8O15.The development of low-cost and high-efficient electrocatalysts toward hydrogen evolution reaction (HER) is highly desirable and challenging. Herein, the novel V-doped Ni3S2/NiS heterostructure nanorod arrays grown on nickel foam (VNS/NF-WM) are synthesized via a facile methanol-assisted hydrothermal method. We demonstrate that the morphology, phase composition, and crystallinity of VNS/NF are well modulated by tuning the ratios of water/methanol solvent. The optimized VNS/NF-WM-heterostructured nanorod (volume ratio of water/methanol is 31) exhibits superior HER electrocatalytic activity with low overpotentials of 85 and 218 mV to yield current density values of 10 and 100 mA cm-2, respectively, meanwhile sustaining an excellent stability with almost an unchanged current density of 10 mA cm-2 for 60 h. Our work offers fresh insights into the rational design of highly active and stable earth-abundant-heterostructured electrocatalysts for the hydrogen fuel production.
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