Thermally-Induced Isomerization of Prenucleation Clusters During the Prenucleation Stage of CdTe Quantum Dots

The evolution of prenucleation clusters in the prenucleation stage of colloidal semiconductor quantum dots (QDs) has remained unexplored. With CdTe as a model system, we show that substances form and isomerize prior to the nucleation and growth of QDs. Called precursor compounds (PCs), the prenucleation clusters are relatively optically transparent and can transform to absorbing magic-size clusters (MSCs). When a prenucleation-stage sample at 25, 45, or 80 °C is dispersed in a mixture of cyclohexane (CH) and octylamine (OTA) at room temperature, either MSC-371, MSC-417, or MSC-448 evolves with absorption peaking at 371, 417, or 448 nm, respectively. We propose that PC-371 forms at 25 °C, and isomerizes to PC-417 at 45 °C and to PC-448 at 80 °C. The PCs and MSCs are quasi isomers. Relatively large and small amounts of OTA favor PC-371 and PC-448 in dispersion, respectively. The present findings suggest the existence of PC-to-PC isomerization in the QD prenucleation stage.     

Observing Confined Local Oxygen-induced Reversible Thiol/Disulfide Cycle with a Protein Nanopore

Disulfide bonds play an important role in thiol-based redox regulation. However, owing to the lack of analytical tools, little is known about how local O₂ mediates the reversible thiol/disulfide cycle under protein confinement. In this study, a protein-nanopore inside a glove box is used to control local O₂ for single-molecule reaction, as well as a single-molecule sensor for real-time monitoring of the reversible thiol/disulfide cycle. The results demonstrate that the local O₂ molecules in protein nanopores could facilitate the redox cycle of disulfide formation and cleavage by promoting a higher fraction of effective reactant collisions owing to nanoconfinement. Further kinetic calculations indicate that the negatively charged residues near reactive sites facilitate proton-involved oxygen-induced disulfide cleavage under protein confinement. The unexpectedly strong oxidation ability of confined local O₂ may play an essential role in cellular redox signaling and enzyme reactions.     

Electroreduction Enables Regioselective 1,2-Diarylation of Alkenes with Two Electrophiles

Precisely introducing two similar functional groups into bulk chemical alkenes represents a formidable route to complex molecules. Especially, the selective activation of two electrophiles is in crucial demand, yet challenging for cross-electrophile-coupling. Herein, we demonstrate a redox-mediated electrolysis, in which aryl nitriles are both aryl radical precursors and redox-mediators, enables an intermolecular alkene 1,2-diarylation with a remarkable regioselectivity, thereby avoiding the involvement of transition-metal catalysts. This transformation utilizes cyanoarene radical anions for activating various aryl halides (including iodides, bromides, and even chlorides) and affords 1,2-diarylation adducts in up to 83 % yield and >20 : 1 regioselectivity with more than 80 examples, providing a feasible approach to complex bibenzyl derivatives.     

Dibenzothiophene Sulfone-Based Ambipolar-Transporting Blue-Emissive Organic Semiconductors Towards Simple-Structured Organic Light-Emitting Transistors

The development of blue-emissive ambipolar organic semiconductor is an arduous target due to the large energy gap, but is an indispensable part for electroluminescent device, especially for the transformative display technology of simple-structured organic light-emitting transistor (SS-OLET). Herein, we designed and synthesized two new dibenzothiophene sulfone-based high mobility blue-emissive organic semiconductors (DNaDBSOs), which demonstrate superior optical property with solid-state photoluminescent quantum yield of 46–67 % and typical ambipolar-transporting properties in SS-OLETs with symmetric gold electrodes. Comprehensive experimental and theoretical characterizations reveal the natural of ambipolar property for such blue-emissive DNaDBSOs-based materials is ascribed to a synergistic effect on lowering LUMO level and reduced electron injection barrier induced by the interfacial dipoles effect on gold electrodes due to the incorporation of appropriate DBSO unit. Finally, efficient electroluminescence properties with high-quality blue emission (CIE (0.179, 0.119)) and a narrow full-width at half-maximum of 48 nm are achieved for DNaDBSO-based SS-OLET, showing good spatial control of the recombination zone in conducting channel. This work provides a new avenue for designing ambipolar emissive organic semiconductors by incorporating the synergistic effect of energy level regulation and molecular-metal interaction, which would advance the development of superior optoelectronic materials and their high-density integrated optoelectronic devices and circuits.     

Nickel-Catalyzed Selective C(sp2)−F Bond Alkylation of Industrially Relevant Hydrofluoroolefin HFO-1234yf

The selective transition-metal catalyzed C−F bond functionalization of inexpensive industrial fluorochemicals represents one of the most attractive approaches to valuable fluorinated compounds. However, the selective C(sp²)−F bond carbofunctionalization of refrigerant hydrofluoroolefins (HFOs) remains challenging. Here, we report a nickel-catalyzed selective C(sp²)−F bond alkylation of HFO-1234yf with alkylzinc reagents. The resulting 2-trifluoromethylalkenes can serve as a versatile synthon for diversified transformations, including the anti-Markovnikov type hydroalkylation and the synthesis of bioactive molecule analogues. Mechanistic studies reveal that lithium salt is essential to promote the oxidative addition of Ni⁰(L_n) to the C−F bond; the less electron-rich N-based ligands, such as bipyridine and pyridine-oxazoline, feature comparable or even higher oxidative addition rates than the electron-rich phosphine ligands; the strong σ-donating phosphine ligands, such as PMe₃, are detrimental to transmetallation, but the less electron-rich and bulky N-based ligands, such as pyridine-oxazoline, facilitate transmetallation and reductive elimination to form the final product.     

N=8 Armchair Graphene Nanoribbons: Solution Synthesis and High Charge Carrier Mobility**

Structurally defined graphene nanoribbons (GNRs) have emerged as promising candidates for nanoelectronic devices. Low band gap (<1 eV) GNRs are particularly important when considering the Schottky barrier in device performance. Here, we demonstrate the first solution synthesis of 8-AGNRs through a carefully designed arylated polynaphthalene precursor. The efficiency of the oxidative cyclodehydrogenation of the tailor-made polymer precursor into 8-AGNRs was validated by FT-IR, Raman, and UV/Vis-near-infrared (NIR) absorption spectroscopy, and further supported by the synthesis of naphtho[1,2,3,4-ghi]perylene derivatives ( 1 and 2 ) as subunits of 8-AGNR , with a width of 0.86 nm as suggested by the X-ray single crystal analysis. Low-temperature scanning tunneling microscopy (STM) and solid-state NMR analyses provided further structural support for 8-AGNR . The resulting 8-AGNR exhibited a remarkable NIR absorption extending up to ∼2400 nm, corresponding to an optical band gap as low as ∼0.52 eV. Moreover, optical-pump TeraHertz-probe spectroscopy revealed charge-carrier mobility in the dc limit of ∼270 cm² V⁻¹ s⁻¹ for the 8-AGNR .     

On-Surface Synthesis and Real-Space Visualization of Aromatic P3N3

On-surface synthesis is at the verge of emerging as the method of choice for the generation and visualization of unstable or unconventional molecules, which could not be obtained via traditional synthetic methods. A case in point is the on-surface synthesis of the structurally elusive cyclotriphosphazene (P₃N₃), an inorganic aromatic analogue of benzene. Here, we report the preparation of this fleetingly existing species on Cu(111) and Au(111) surfaces at 5.2 K through molecular manipulation with unprecedented precision, i.e., voltage pulse-induced sextuple dechlorination of an ultra-small (about 6 Å) hexachlorophosphazene P₃N₃Cl₆ precursor by the tip of a scanning probe microscope. Real-space atomic-level imaging of cyclotriphosphazene reveals its planar D_3h-symmetric ring structure. Furthermore, this demasking strategy has been expanded to generate cyclotriphosphazene from a hexaazide precursor P₃N₂₁ via a different stimulation method (photolysis) for complementary measurements by matrix isolation infrared and ultraviolet spectroscopy.     

Azodicarboxylate-Mediated Peptide Cyclisation: Application to Disulfide Bond Formation in Solution and Solid Phase

Cyclic peptides are important molecules, playing key roles in protein architecture, as chemical probes, and increasingly as crucial structural elements of clinically-useful therapeutics. Herein we report methodology using azodicarboxylates as efficient reagents for the facile synthesis of cyclic peptides through a disulfide bridge. The utility of this approach in both solution and solid-phase, and compatibility with common amino acid side chain functionalities is demonstrated, resulting in cyclic peptides in good yield and purity. This approach has significant potential application for synthesis of molecules of biological or therapeutic significance.     

Zn2+@Polyvinylpyrrolidone and Urushiol Preparation of Nanofibrous Membranes and Their Synergistic Effect

In this study, lacquer is gathered from a lacquer tree and rotary evaporation is used to remove impurities to obtain urushiol. Next, 10 mL of anhydrous ethanol serves as the solvent for blending polyvinylpyrrolidone (PVP) at a specified content (0.7 g and 0.2–0.7 g urushiol) to form an electrospinning solution. Electrospinning is carried out with a voltage of 18 kV to prepare PVP/urushiol nanofibrous membranes. At a ratio of 7/4, the PVP/urushiol nanofibrous membranes are not eroded in 98% sulfuric acid and these membranes also demonstrate a 50–60% antibacterial effect against Staphylococcus aureus and Escherichia coli. Moreover, the antibacterial effect can be boosted to 98% with the incorporation of zinc ions. The results indicate that anhydrous ethanol can remove the sensitization of urushiol from PVP/urushiol membranes. Furthermore, animal test results indicate that when rats are in contact with PVP/urushiol anhydrous ethanol for 48 h, their skins are free from dark brown skin allergy. The presence of PVP eliminates the sensitization of urushiol, and the nanofibrous membranes demonstrate low toxicity. Hence, urushiol is the only natural material that enables PVP to withstand 98% sulfuric acid as well as acquire hydrolyzability, thereby qualify PVP as a medical material.     

Correlation between Interfacial Structures and Device Performance: The Double-Edged Sword Effect of Lead Iodide in Perovskite Solar Cells

The interfacial electronic structure of perovskite layers and transport layers is critical for the performance and stability of perovskite solar cells (PSCs). The device performance of PSCs can generally be improved by adding a slight excess of lead iodide (PbI₂) to the precursor solution. However, its underlying working mechanism is controversial. Here, we performed a comprehensive study of the electronic structures at the interface between CH₃NH₃PbI₃ and C₆₀ with and without the modification of PbI₂ using in situ photoemission spectroscopy measurements. The correlation between the interfacial structures and the device performance was explored based on performance and stability tests. We found that there is an interfacial dipole reversal, and the downward band bending is larger at the CH₃NH₃PbI₃/C₆₀ interface with the modification of PbI₂ as compared to that without PbI₂. Therefore, PSCs with PbI₂ modification exhibit faster charge carrier transport and slower carrier recombination. Nevertheless, the modification of PbI₂ undermines the device stability due to aggravated iodide migration. Our findings provide a fundamental understanding of the CH₃NH₃PbI₃/C₆₀ interfacial structure from the perspective of the atomic layer and insight into the double-edged sword effect of PbI₂ as an additive.