Highly Selective Binding and Inhibition of Pyr-His-Pro-NH2 (TRH) Function using a Polypyridinyl Macrocyclic Receptor with an Amphiphilic Cavity.

Macrocycle, cyclo[4] [(1,3-(4,6)-dimethylbezene)[4](2,6-(3,5)-dimethylpyridine (B4P4), shows highly selective binding affinity with protirelin (Pyr-His-Pro-NH2 ; TRH) among the tested 26 drug or drug adductive substrates. The stable complexation in a 1:1 manner was fully characterized in solution, gas phase, and solid state study. Furthermore, B4P4 acts as an efficient TRH inhibitor even at [macrocycle]:[drug] <1:300, both in membrane transport and cellar incubation. The current work provides an unprecedented strategy for macrocycles to be efficiently used in drug target therapy.

Research on energy-saving factors adaptability of exterior envelopes of university teaching-office buildings under different climates (China) based on orthogonal design and EnergyPlus.

To achieve carbon neutrality in 2060 (China), building energy-saving has been highly concerned. University buildings have great energy-saving potential as part of energy consumption where 70% of energy loss is caused by heat transfer from the envelope. However, most of the research on energy-saving factors for envelopes is limited to a certain climate or a specific building type, and the optimal configuration of envelopes under different climatic regions has not been well solved. Therefore, the influence degree and appropriate parameters of each factor of the teaching-office building envelopes on energy consumption under different climates were analyzed in this paper by orthogonal design and numerical simulation. Results show that: (1) Solar heat gain coefficient (SHGC) and indoor air change rates (ACH) [the heat transfer coefficient of the exterior wall (K wall ) and ACH] are the main factors affecting the cooling [heating] load, the insulation form of the exterior wall (W ins ) and K wall [W ins and solar radiation absorption coefficient of exterior surface materials (ρ s )] have less influence; (2) The important ranking and optimal level of the influence of each factor on the cooling (or heating) loads are related to local load demands; (3) For the annual load, K wall and the heat transfer coefficient of the exterior window (K win ) is the focus of energy-saving in severe cold and cold zones, but their impact is not significant in Guangzhou and Kunming, and the high significance of SHGC is only shown in Hohhot, Lhasa, Guangzhou, and Haikou; (4) The annual load energy savings reach 39.64%-57.57% in different climates by optimizing all factors. The research results can provide directions and data references for the energy-saving design and renovation of educational building envelopes in different climates (China).

Constructing Heterogeneous Direct Z-Scheme Photocatalysts Based on Metal-Organic Cages and Graphitic-C3N4 for High-Efficiency Photocatalytic Water Splitting.

The development of artificial devices that mimic the highly efficient and ingenious photosystems in nature is worthy of in-depth study. A metal-organic cage (MOC) Pd2(M-4)4(BF4)4, denoted as MOC-Q1, integrating four organic photosensitized ligands M-4 and two Pd2+ catalytic centers is designed for a photochemical molecular device (PMD). MOC-Q1 is successfully immobilized on graphitic carbon nitride (g-C3N4) by hydrogen bonds to obtain a robust heterogeneous direct Z-scheme g-C3N4/MOC-Q1 photocatalyst for H2 generation under visible light. The optimized g-C3N4/MOC-Q1 (2 wt %) system shows high hydrogen evolution activity (4495 µmol g-1 h-1 based on the catalyst mass) and exhibits stable performances for 25 h (a turnover number of 19,268 based on MOC-Q1), significantly outperforming pure MOC-Q1, g-C3N4, and comparsion materials Pd/g-C3N4/M-4, which is the highest one of all reported heterogeneous MOC-based photocatalysts under visible irradiation. This enhancement can be ascribed to the synergistic effects of high-efficient electron transfer, extended visible-light response region, and good protective environment for MOC-Q1 arising from an efficient direct Z-scheme heterostructure of g-C3N4/MOC-Q1. This rationally designed and synthesized MOC/g-C3N4-based heterogeneous PMD is expected to have great potential in photocatalytic water splitting.

Robust Heterogeneous Photocatalyst for Visible-Light-Driven Hydrogen Evolution Promotion: Immobilization of a Fluorescein Dye-Encapsulated Metal-Organic Cage on TiO2.

The design of artificial photocatalytic devices that simulates the ingenious and efficient photosynthetic systems in nature is promising. Herein, a metal-organic cage [Pd6(NPyCzPF)12]12+ (MOC-PC6) integrating 12 organic ligands NPyCzBP and 6 Pd2+ catalytic centers is designed, which is well defined to include organic dye fluorescein (FL) for constructing a supramolecular photochemical molecular device (SPMD) FL@MOC-PC6. Photoinduced electron transfer (PET) between MOC-PC6 and the encapsulated FL has been observed by steady-state and time-resolved emission spectroscopy. FL@MOC-PC6 is successfully heterogenized with TiO2 by a facile sol-gel method to achieve a robust heterogeneous FL@MOC-PC6-TiO2. The close proximity between the Pd2+ catalytic site and FL included in the cage enables PET from the photoexcited FL to Pd2+ sites through a powerful intramolecular pathway. The photocatalytic hydrogen production assessments of the optimized 4 wt % FL@MOC-PC6-TiO2 demonstrate an initial H2 production rate of 2402 µmol g-1 h-1 and a turnover number of 4356 within 40 h, enhanced by 15-fold over that of a homogeneous FL@MOC-PC6. The effect of the MOC content on photocatalytic H2 evolution (PHE) is investigated and the inefficient comparison systems, such as MOC-PC6, MOC-PC6-TiO2, FL-sensitized MOC-PC6/FL-TiO2, and analogue FL/MOC-PC6-TiO2 with free FL, are evaluated. This study provides a creative and distinctive approach for the design and preparation of novel heterogeneous SPMD catalysts based on MOCs.