Pd-catalyzed cascade cyclization of allenylethylene carbonates and indandiones: Synthesis of tetracyclic dihydrocyclopentaindenofuranone derivatives

A palladium-catalyzed cascade cyclization of allenylethylene carbonates with 1,3-indandiones was developed, providing biologically interesting tetracyclic dihydrocyclopentaindenofuranone derivatives having three contiguous quaternary carbon centers in moderate to high yields with excellent diastereoselectivities. In this reaction, the allene moiety was fully fused into the cyclopentene ring.     

Scalable and Robust Bio-inspired Organogel Coating by Spraying Method Towards Dynamic Anti-scaling

Scaling usually causes serious problems in daily life and industrial production. Currently, developing passive anti-scaling coatings has shown promises to overcome this problem. In this work, we fabricated a scalable and robust bio-inspired organogel(BIO) coating, showing dynamic scale resistance in the oil/brine mixture. The oil layer of the BIO coating was utilized as a barrier to inhibit scale nucleation and reduce scale adhesion. The mechanical strength of the coating was optimized by regulating nanoparticle contents. Moreover, the universality of scale resistance was demonstrated by varying the types of nanoparticles, oils and scales. Compared with commercial pipeline materials, such as copper, this BIO coating significantly reduces scale deposition after 240-h scaling test(ca. 93% reduction). Therefore, this study designs scalable and robust organogel coatings for sustainable scale resistance, which may be used for practical application in oil production.     

Noble metal nanoparticles meet molecular cages: A tale of integration and synergy

Noble metal nanoparticles attract growing interest owing to their high surface-to-volume ratio and unique optical, electric and catalytic properties. Fine-tuning these properties and broadening potential applications can be envisaged if nanoparticles are coupled to supramolecular cages that afford a highly tailorable inner environment as well as rich endo-/exo-functionalization. Due to rich chemical/physical properties of cages, integration of multiple host-guest interactions in confined cavities through endo-molecular design has been achieved. Such cages provide ideal confined templates for size-controlled synthesis of ultrafine nanoparticles with superior catalytic activities. Moreover, exo-functionalization of cages offers huge opportunities to couple with nanoparticles, generating cage-nanoparticle hybrids or hierarchical assemblies that combine merits of both. The present review provides recent advances in cage-mediated nanoparticle systems with synergistic effects and integrated functions, and demonstrates their applications in catalysis, sensing, chiral amplification, plasmonic switches, imaging and cell therapy. Finally, we highlight key challenges and identify emerging directions in the coming years.     

Functional Peptides from One-bead One-compound High-throughput Screening Technique

Combinatorial chemistry provides a cost-effective method for the rapid discovery of new functional peptides. One-bead one-compound(OBOC) high-throughput screening technique offers a lot of structurally diverse peptides to be rapidly synthesized and screened for binding to a target of interest. The OBOC peptide library screening involves three main steps: library construction, positive beads separation, and peptide sequencing. This review mainly summarizes some special technique tips during functional peptide screening and potential future directions of the OBOC high-throughput screening technique.     

Unveiling the High-valence Oxygen Degradation Across the Delithiated Cathode Surface

Charge compensation on anionic redox reaction (ARR) has been promising to realize extra capacity beyond transition metal redox in battery cathodes. The practical development of ARR capacity has been hindered by high-valence oxygen instability, particularly at cathode surfaces. However, the direct probe of surface oxygen behavior has been challenging. Here, the electronic states of surface oxygen are investigated by combining mapping of resonant Auger electronic spectroscopy (mRAS) and ambient pressure X-ray photoelectron spectroscopy (APXPS) on a model LiCoO₂ cathode. The mRAS verified that no high-valence oxygen can sustain at cathode surfaces, while APXPS proves that cathode electrolyte interphase (CEI) layer evolves and oxidizes upon oxygen gas contact. This work provides valuable insights into the high-valence oxygen degradation mode across the interface. Oxygen stabilization from surface architecture is proven a prerequisite to the practical development of ARR active cathodes.     

Manganese-Catalyzed Hydrogenative Desulfurization of Thioamides

Earth-abundant transition metal catalysis has emerged as an important alternative to noble transition metal catalysis in hydrogenation reactions. However, there has been no Earth-abundant transition metal catalyzed hydrogenation of thioamides reported so far, presumably due to the poisoning of catalysts by sulfur-containing molecules. Herein, we described the first manganese-catalyzed hydrogenative desulfurization of thioamides to amines or imines. The key to success is the use of MnBr(CO)₅ instead of commonly-employed pincer-manganese catalysts, together with simple NEt₃ and CuBr. This protocol features excellent selectivity on sole cleavage of the C=S bond of thioamides, in contrast to the only known Ru-catalyzed hydrogenation of thioamides, and unprecedented chemo-selectivity tolerating vulnerable functional groups such as nitrile, ketone, aldehyde, ester, sulfone, nitro, olefin, alkyne and heterocycle, which are usually susceptible to common hydride-type reductive protocols.     

Enhancing Built-in Electric Fields for Efficient Photocatalytic Hydrogen Evolution by Encapsulating C60 Fullerene into Zirconium-Based Metal-Organic Frameworks

High-efficiency photocatalysts based on metal-organic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C₆₀ into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in C₆₀@NU-901. The direct consequence is a robust built-in electric field, which tends to be 10.7 times higher in C₆₀@NU-901 than that found in NU-901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g⁻¹ h⁻¹ for C₆₀@NU-901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host-guest interactions constitutes a promising strategy to design photocatalysts for efficient solar-to-chemical energy conversion.     

Dredging the Charge-Carrier Transfer Pathway for Efficient Low-Dimensional Ruddlesden-Popper Perovskite Solar Cells

Low-dimensional Ruddlesden-Popper (LDRP) perovskites still suffer from inferior carrier transport properties. Here, we demonstrate that efficient exciton dissociation and charge transfer can be achieved in LDRP perovskite by introducing γ-aminobutyric acid (GABA) as a spacer. The hydrogen bonding links adjacent spacing sheets in (GABA)₂MA₃Pb₄I₁₃ (MA=CH₃NH₃⁺), leading to the charges localized in the van der Waals gap, thereby constructing “charged-bridge” for charge transfer through the spacing region. Additionally, the polarized GABA weakens dielectric confinement, decreasing the (GABA)₂MA₃Pb₄I₁₃ exciton binding energy as low as ≈73 meV. Benefiting from these merits, the resultant GABA-based solar cell yields a champion power conversion efficiency (PCE) of 18.73 % with enhanced carrier transport properties. Furthermore, the unencapsulated device maintains 92.8 % of its initial PCE under continuous illumination after 1000 h and only lost 3 % of its initial PCE under 65 °C for 500 h.     

Minimizing Temperature Bias through Reliable Temperature Determination in Gas-Solid Photothermal Catalytic Reactions

Enormous advances in photothermal catalysis have been made over the years, whereas the temperature assessment still remains controversial in the majority of photothermal catalytic systems. Herein, we methodically uncovered the phenomenon of temperature determination bias arising from prominent temperature differences in gas-solid photothermal catalytic systems, which extensively existed yet has been overlooked in most relevant cases. To avoid the interference of temperature bias, we developed a universal protocol for reliable temperature evaluation of gas-solid photothermal catalytic reactions, with emphasis on eliminating the temperature gradient and temperature fluctuation of catalyst layer via optimizing the reaction system. This work presents a functional and credible practice for temperature detection, calling attention to addressing the effects of temperature differences, and reassessing the actual temperature-based performances in gas-solid photothermal catalysis.     

Selective In Situ Analysis of Mature microRNAs in Extracellular Vesicles Using a DNA Cage-Based Thermophoretic Assay

Mature microRNAs (miRNAs) in extracellular vesicles (EVs) are involved in different stages of cancer progression, yet it remains challenging to precisely detect mature miRNAs in EVs due to the presence of interfering RNAs (such as longer precursor miRNAs, pre-miRNAs) and the low abundance of tumor-associated miRNAs. By leveraging the size-selective ability of DNA cages and polyethylene glycol (PEG)-enhanced thermophoretic accumulation of EVs, we devised a DNA cage-based thermophoretic assay for highly sensitive, selective, and in situ detection of mature miRNAs in EVs with a low limit of detection (LoD) of 2.05 fM. Our assay can profile EV mature miRNAs directly in serum samples without the interference of pre-miRNAs and the need for ultracentrifugation. A clinical study showed that EV miR-21 or miR-155 had an overall accuracy of 90 % for discrimination between breast cancer patients and healthy donors, which outperformed conventional molecular probes detecting both mature miRNAs and pre-miRNAs. We envision that our assay can advance EV miRNA-based diagnosis of cancer.