Photoinduced [3 + 2] Cycloadditions of Aryl Cyclopropyl Ketones with Alkynes and Alkenes.

The five-membered ring skeleton is one of the most pivotal in the area of pharmaceutical and natural products. [3 + 2] cycloadditions of cyclopropyl and unsaturated compounds are a highly efficient and atom-economical way to build a five-member compound. The previous works about the kind of [3 + 2] cycloadditions usually utilized metal or organic small molecule catalysts. However, an ideal [3 + 2] cycloaddition reaction that smoothly happens without any additives and catalysts under mild conditions is underdeveloped. Hence, we report [3 + 2] cycloadditions of aryl cyclopropyl without any additives and catalysts under purple LED. In this method, a broad scope of cyclopropyl, alkyne, and alkene was very compatible, especially drug derivatives ibuprofen and Ioxoprofen, to obtain the corresponding cycloaddition product with a good yield up to 93%.

Simultaneously Regulated Highly Polarized and Long-Lived Valley Excitons in WSe2/GaN Heterostructures.

Interlayer excitons, with prolonged lifetimes and tunability, hold potential for advanced optoelectronics. Previous research on the interlayer excitons has been dominated by two-dimensional heterostructures. Here, we construct WSe2/GaN composite heterostructures, in which the doping concentration of GaN and the twist angle of bilayer WSe2 are employed as two ingredients for the manipulation of exciton behaviors and polarizations. The exciton energies in monolayer WSe2/GaN can be regulated continuously by the doping levels of the GaN substrate, and a remarkable increase in the valley polarizations is achieved. Especially in a heterostructure with 4°-twisted bilayer WSe2, a maximum polarization of 38.9% with a long lifetime is achieved for the interlayer exciton. Theoretical calculations reveal that the large polarization and long lifetime are attributed to the high exciton binding energy and large spin flipping energy during depolarization in bilayer WSe2/GaN. This work introduces a distinctive member of the interlayer exciton with a high degree of polarization and a long lifetime.

Manipulations of Electronic and Spin States in Co-Quantum Dot/WS2 Heterostructure on a Metal-Dielectric Composite Substrate by Controlling Interfacial Carriers.

Charge and spin are two intrinsic attributes of carriers governing almost all of the physical processes and operation principles in materials. Here, we demonstrate the manipulation of electronic and spin states in designed Co-quantum dot/WS2 (Co-QDs/WS2) heterostructures by employing a metal-dielectric composite substrate and via scanning tunneling microscope. By repeatedly scanning under a unipolar bias, switching the bias polarity, or applying a pulse through nonmagnetic or magnetic tips, the Co-QDs morphologies exhibit a regular and reproducible transformation between bright and dark dots. First-principles calculations reveal that these tunable characters are attributed to the variation of density of states and the transition of magnetic anisotropy energy induced by carrier accumulation. It also suggests that the metal-dielectric composite substrate is successful in creating the interfacial potential for carrier accumulation and realizes the electrically controllable modulations. These results will promote the exploration of electron-matter interactions in quantum systems and provide an innovative way to facilitate the development of spintronics.

Photoinduced iron-catalyzed C-H alkylation of polyolefins.

Chemically introducing diverse polar groups into polyolefins via carbon-hydrogen bond alkylation with polar olefins is of substantial value in the synthesis of next-generation lightweight thermoplastics, which is still underdeveloped. In this work, we report a new approach for efficient carbon-hydrogen bond alkylation in commodity polyolefins using photoinduced iron catalysis. Various polyolefins could be functionalized with broad scope. Polar groups could be incorporated in a single step. The controllable synthesis of multi-polar functional polyolefins could be achieved by a designed module-assembled process. Remarkably, even low levels of functionalization could upcycle the polyolefin materials to exhibit unusual physical properties, such as enhancement of the transparencies, strains, stresses at break of the materials, and hydrophilicity.

Controllable C-H Alkylation of Polyethers via Iron Photocatalysis.

The efficient conversion of a C-H bond in the polyether chain to other functional groups provides great opportunities for development of novel applications in many research fields. However, this field is quite underdeveloped due to the key challenge on controlling the selectivity of the C-H bond functionalization over the chain cleavage. In this work, we report a controllable C-H bond alkylation of polyethers under mild conditions via photoinduced iron catalysis. The level of functionalization could be controlled by using different amounts of alkenes and various reaction times, while the molecular weight distributions were maintained narrow. A broad scope of electron-deficient alkenes containing nitrile, ester, epoxide, terminal alkynyl, 2,5-dioxotetrafuranyl, and 2,5-dioxopyrrolidinyl groups could be utilized to functionalize the different polyethers with great efficiencies. The potential applications of the modified polyethylene glycols and polyethylene oxides were explored by the preparation of novel hydrogels and solid-state electrolytes with enhancement of lithium ion conductivities. Moreover, the density functional theory calculation disclosed the plausible mechanism and explained the high selectivity for the C-H alkylation.

Integrated energy system optimal scheduling considering the comprehensive and flexible operation mode of pumping storage.

The integrated energy system (IES) optimal scheduling under the comprehensive flexible operation mode of pumping storage is considered. This system is conducive to the promotion of the accommodation of wind and solar energy and can meet the water, electricity and heat needs of coastal areas far away from the energy center. In this study, the joint dispatch between double pumped storage power stations is used to accommodate wind and solar energy better and smooth their fluctuations on the grid. Through the scheduling of water between the high and low reservoirs of double pumped storage power stations and the reservoir of the seawater desalination plant, the impact of storage capacity constraints on pumped storage power plants is reduced. Moreover, the objective function to build the IES optimization scheduling model is to achieve minimum economic cost. The results reveal that the integrated energy system accommodates all wind energy and solar energy. As such, the system increases the average working time of the pumped storage unit by 1.9 hours and reduces the economic cost by 31.50%. Based on the simulation results, the model can enhance the accommodation capability of wind energy and solar energy and improve the system economy.

Optimal scheduling of integrated energy system based on improved grey wolf optimization algorithm.

The optimal scheduling problem of integrated energy system (IES) has the characteristics of high-dimensional nonlinearity. Using the traditional Grey Wolf Optimizer (GWO) to solve the problem, it is easy to fall into a local optimum in the process of optimization, resulting in a low-quality scheduling scheme. Aiming at the dispatchability of electric and heat loads, this paper proposes an electric and heat comprehensive demand response model considering the participation of dispatchers. On the basis of incentive demand response, the group aggregation model of electrical load is constructed, and the electric load response model is constructed with the goal of minimizing the deviation between the dispatch signal and the load group aggregation characteristic model. Then, a heat load scheduling model is constructed according to the ambiguity of the human body's perception of temperature. On the basis of traditional GWO, the Fuzzy C-means (FCM) clustering algorithm is used to group wolves, which increases the diversity of the population, uses the Harris Hawk Optimizer (HHO) to design the prey to search for the best escape position, and reduces the local The optimal probability, and the use of Particle Swarm Optimizer (PSO) and Bat Optimizer (BO) to design the moving modes of different positions, increase the ability to find the global optimum, so as to obtain an Improved Gray Wolf Optimizer (IGWO), and then efficiently solve the model. IGWO can improve the defect of insufficient population diversity in the later stage of evolution, so that the population diversity can be better maintained during the entire evolution process. While taking into account the speed of optimization, it improves the algorithm's ability to jump out of the local optimum and realizes continuous deep search. Compared with the traditional intelligent Optimizer, IGWO has obvious improvement and achieved better results. At the same time, the comprehensive demand response that considers the dispatcher's desired signal improves the accommodation of new energy and reduces the operating cost of the system, and promotes the benign interaction between the source and the load.

Photoinduced Ligand-to-Metal Charge Transfer (LMCT) of Fe Alkoxide Enabled C-C Bond Cleavage and Amination of Unstrained Cyclic Alcohols.

We report an alkoxy radical process for the C-C bond cleavage and functionalization of unstrained tertiary and secondary cyclic alcohols. In the absence of a chlorine atom, the readily available iron catalysts [Fe(OBu-t)3 or Fe(acac)3/t-BuONa] facilitate alkoxy radical formation via the direct ligand-to-metal charge transfer of Fe alkoxide and further enable the ring opening and amination of cyclic alcohols. The remote amino carbonyl compounds could be obtained with a broad scope in up to excellent yields under the mildly redox-neutral system. Light-driven electron transfer, alkoxy radical formation, and subsequent C-C bond cleavage via ß-scission were the keys to the transformation.

Oxidative α-C-C Bond Cleavage of 2° and 3° Alcohols to Aromatic Acids with O2 at Room Temperature via Iron Photocatalysis.

The selective α-C-C bond cleavage of unfunctionalized secondary (2°) and tertiary alcohols (3°) is essential for valorization of macromolecules and biopolymers. We developed a blue-light-driven iron catalysis for aerobic oxidation of 2° and 3° alcohols to acids via α-C-C bond cleavages at room temperature. The first example of oxygenation of the simple tertiary alcohols was reported. The iron catalyst and blue light play critical roles to enable the formation of highly reactive O radicals from alcohols and the consequent two α-C-C bond cleavages.

Alkali-etching growth of nest-like Ag@mTiO2 hierarchical nanostructures and their potential applications.

Porous nanomaterials have attracted extensive interests in adsorption, catalysis, biosensors, and biomedicine due to their high surface area, well-defined pore structure and tunable pore size. However, how to obtain porous nanomaterials of desirable component and unique structure with multifunctionalities and synergetic properties is still a great challenge. In this work, a novel nest-like Ag@mTiO2 hierarchical nanostructure with Ag nanoparticle as the core and a mesoporous crystalline TiO2 as the protective shell was successfully prepared by layer-by-layer assembly technique and alkali-etching hydrothermal route. By simply changing the conditions of alkali etching, different nanostructures could be obtained, such as core-shell or rattle type. In the process, the thickness of coating silica layer and TiO2 shell both played important roles for the formation of desired nanostructures. The as-prepared products had a large specific surface area of 301m2/g and a tailored TiO2 outer shell. Raman spectra results showed perfect SERS signal of the tags enhanced and remained good stability even after one month. Doxycycline (Doxy) was chosen to evaluate their drug loading and controlled release properties. The results indicated that the obtained Ag@mTiO2 nanoparticles exhibited good biocompatibility and excellent drug-loading capacity. Consequently, they are also expected to serve as ideal candidates for more potential applications including photocatalysis, drug controlled release, biosensor and cell imaging, etc.