Electrophotochemical Ce-Catalyzed Ring-Opening Functionalization of Cycloalkanols under Redox-Neutral Conditions: Scope and Mechanism.

Selective cleavage and functionalization of C-C bonds in alcohols is gaining increasing interest in organic synthesis and biomass conversion. In particular, the development of redox-neutral catalytic methods with cheap catalysts and clean energy is of utmost interest. In this work, we report a versatile redox-neutral method for the ring-opening functionalization of cycloalkanols by electrophotochemical (EPC) cerium (Ce) catalysis. The EPC-Ce-enabled catalysis allows for cycloalkanols with different ring sizes to be cleaved while tolerating a broad range of functional groups. Notably, in the presence of chloride as a counteranion and electrolyte, this protocol selectively leads to the formation of C-CN, C-C, C-S, or C-oxime bonds instead of a C-halide bond after ß-scission. A preliminary mechanistic investigation indicates that the redox-active Ce catalyst can be tuned by electro-oxidation and photo-reduction, thus avoiding the use of an external oxidant. Spectroscopic characterizations (cyclic voltammetry, UV-vis, electron paramagnetic resonance, and X-ray absorption fine structure) suggest a Ce(III)/Ce(IV) catalytic pathway for this transformation, in which a Ce(IV)-alkoxide is involved.

Effect of fitness exercise on risk assessment of mental and emotional health

The study aims to investigate the effect of physical activity on risk assessment for mental and emotional health. This paper studies the psychological test assessment through the psychological health risk assessment and psychological crisis intervention for college students and the psychological health crisis counselling risk assessment system. Experiments show that the evaluation accuracy of the designed system can reach 99% at most, and the detection time is at least 5S, which improves the evaluation performance. Based on the evaluation and with an emphasis on prevention, we will deconstruct the connotation of life education, build and operate a college students' mental health early warning system, and scientifically adopt psychological crisis intervention strategies and technologies to establish a college students' psychological crisis intervention mechanism and to promote and maintain college students' mental health.(AU)

Tuning the reactivity of alkoxyl radicals from 1,5-hydrogen atom transfer to 1,2-silyl transfer.

Controlling the reactivity of reactive intermediates is essential to achieve selective transformations. Due to the facile 1,5-hydrogen atom transfer (HAT), alkoxyl radicals have been proven to be important synthetic intermediates for the δ-functionalization of alcohols. Herein, we disclose a strategy to inhibit 1,5-HAT by introducing a silyl group into the α-position of alkoxyl radicals. The efficient radical 1,2-silyl transfer (SiT) allows us to make various α-functionalized products from alcohol substrates. Compared with the direct generation of α-carbon radicals from oxidation of α-C-H bond of alcohols, the 1,2-SiT strategy distinguishes itself by the generation of alkoxyl radicals, the tolerance of many functional groups, such as intramolecular hydroxyl groups and C-H bonds next to oxygen atoms, and the use of silyl alcohols as limiting reagents.

Quantum Confinement-Tunable Ultrafast Charge Transfer in a PbS Quantum Dots/WSe2 0D-2D Hybrid Structure: Transition from the Weak to Strong Coupling Regime.

0D-2D mixed-dimensional hybrid structures, which combine tunable optical properties of 0D quantum dots (QDs) and high transport mobilities of 2D layered materials, have shown great potential in optoelectronic applications. Understanding charge transfer dynamics at the 0D-2D interface is essential but still lacking. Here, using PbS QD/WSe2 system, by simply controlling PbS QD size, we show a tunable hole transfer (HT) rate by more than 4 orders of magnitude (from ∼1 ns to <100 fs) and, interestingly, transition from the weak to strong coupling regime due to quantum confinement effect. In contrast to reported layer-dependent energy transfer dynamics, we observe a robust HT rate against WSe2 layer number, which can be ascribed to a subtle change of WSe2 valence band structure with layer number. Our results are important to not only fundamental understanding of charge transfer behavior at nanoscale low-dimensional interface but also help design next-generation mixed-dimensional optoelectronic devices.

Heavily Doped Semiconductor Colloidal Nanocrystals as Ultra-Broadband Switches for Near-Infrared and Mid-Infrared Pulse Lasers.

Heavily self-doped semiconductors can be designed to be used in advanced photonics due to both fabrication and functional advantages. Ultrafast response, strong optical nonlinearity, broadband wavelength range, and accessibility of integration are major challenges for ultrafast all-optical photonics to operate in the infrared wavelength range. Here, solution-processed Cu1.8Se semiconductor nanocrystals (NCs) demonstrate an ultrafast response (about 360-520 fs), strong optical nonlinearity (as large as -1.4 × 103 cm GW-1), and broadband (from 800 to 3000 nm) nonlinear optical absorption in the near-infrared and mid-infrared wavelength ranges. The ultrafast response and larger optical nonlinearity may be triggered by the plasma ground-state bleaching in the strong surface electromagnetic filed. Stable Q-switched lasers in Er-doped fiber laser, Tm-doped fiber laser, and Ho/Pr-codoped ZBLAN fiber laser are operated, respectively. These findings indicate that Cu1.8Se NCs are prospective nonlinear materials for ultrafast response and broadband pulse laser.

Ultrafast self-trapping of photoexcited carriers sets the upper limit on antimony trisulfide photovoltaic devices.

Antimony trisulfide (Sb2S3) is considered to be a promising photovoltaic material; however, the performance is yet to be satisfactory. Poor power conversion efficiency and large open circuit voltage loss have been usually ascribed to interface and bulk extrinsic defects By performing a spectroscopy study on Sb2S3 polycrystalline films and single crystal, we show commonly existed characteristics including redshifted photoluminescence with 0.6 eV Stokes shift, and a few picosecond carrier trapping without saturation at carrier density as high as approximately 1020 cm-3. These features, together with polarized trap emission from Sb2S3 single crystal, strongly suggest that photoexcited carriers in Sb2S3 are intrinsically self-trapped by lattice deformation, instead of by extrinsic defects. The proposed self-trapping explains spectroscopic results and rationalizes the large open circuit voltage loss and near-unity carrier collection efficiency in Sb2S3 thin film solar cells. Self-trapping sets the upper limit on maximum open circuit voltage (approximately 0.8 V) and thus power conversion efficiency (approximately 16 %) for Sb2S3 solar cells.

Ultrafast and broadband optical nonlinearity in aluminum doped zinc oxide colloidal nanocrystals.

Heavily doped oxide semiconductors can be tailored for widespread application in near-infrared (NIR) and mid-infrared (mid-IR) wavelength ranges because of both functional and fabrication advantages. Here, the ultrafast and broadband nonlinear saturable absorption of Al-doped zinc oxide nanocrystals (AZO NCs) is investigated by using the Z-scan technique and the pump-probe technique. The nonlinear absorption coefficient is as high as -1.90 × 103 cm GW-1 in the wide infrared (IR) wavelength range (from 800 to 3000 nm). Furthermore, a maximum optically induced refractive index of -1.85 × 10-1 cm2 GW-1 in the dielectric region and 2.09 × 10-1 cm2 GW-1 in the metallic region leads to an ultrafast nonlinear optical response (less than 350 femtoseconds). Mode-locked fiber lasers at 1064 nm and 1550 nm as well as Q-switched fiber lasers near 2000 nm and 3000 nm prove the use of employing AZO NCs as a broadband and ultrafast nonlinear optical device, which provides a valuable strategy and intuition for the development of nanomaterial-based photonic and optoelectronic devices in the NIR and mid-IR wavelength ranges.

Supramolecular Solid-State Microlaser Constructed from Pillar[5]arene-Based Host-Guest Complex Microcrystals.

Herein we report a novel host-guest complex single crystal material based on a pillar[5]arene (P5) and a laser dye trans-4-[ p-(dimethylamino)styryl]-1-methylpyridinium iodide (DASP). Single crystal structure characterization shows that two P5 molecules act as a supramolecular nanocapsule for one isolated DASP molecule. This spatial confinement effectively restricts aggregation-caused quenching (ACQ) effects and other nonradiative channels (e.g., twisted intramolecular charge transfer), leading to high luminescent efficiency of the isolated DASP. Together with its regular shape and smooth surface, each 2P5⊃DASP microcrystal forms a Fabry-Pérot (F-P) microcavity and produces a stable laser output with a high Q factor and a low threshold.

Synthesis and anti-cancer activity evaluation of novel prenylated and geranylated chalcone natural products and their analogs.

Four natural chalcones bearing prenyl or geranyl groups, i.e., bavachalcone (1a), xanthoangelol (1b), isobavachalcone (1c), and isoxanthoangelol (1d) were synthesized by using a regio-selective iodination and the Suzuki coupling reaction as key steps. The first total synthesis of isoxanthoangelol (1d) was achieved in 36% overall yield. A series of diprenylated and digeranylated chalcone analogs were also synthesized by alkylation, regio-selective iodination, aldol condensation, Suzuki coupling and [1,3]-sigmatropic rearrangement. The structures of the 11 new derivatives were confirmed by (1)H NMR, (13)C NMR and HRMS. The anticancer activity of these new chalcone derivatives against human tumor cell line K562 were evaluated by MTT assay in vitro. SAR studies suggested that the 5'-prenylation/geranylation of the chalcones significantly enhance their cytotoxic activity. Among them, Bavachalcone (1a) displayed the most potent cytotoxic activity against K562 with IC50 value of 2.7 µM. The morphology changes and annexin-V/PI staining studies suggested that those chalcone derivatives inhibited the proliferation of K562 cells by inducing apoptosis.