From in situ AFM measurements, we found a dimension of a unit cell in the self-assembled structure and proposed a model of lattice matching between peptides and MoS2 lattice. The lattice matching for chiral recognition was further investigated by changing peptide sequences and surface lattice from MoS2 to graphite. This work further deepened the understanding of biomolecular chiral recognition and will lead us to rationally design specific morphologies and conformations of chiral self-assembled structures of peptides with expected functions in the future.Historically often described as the food of gods, cocoa-based products exhibit a pleasant aroma as well as a desirable astringent, bitter, and sour taste, which results in a high consumer preference. The key taste components of cocoa were identified and characterized by combining sensory analysis, fractionation, and structure elucidation. Cocoa astringency is driven by N-phenylpropenoyl-l-amino acids, polyphenol glycosides, and flavan-3-ols, while the latter compound class also contributes to bitterness. The key principle for cocoa bitterness was shown to be the combination of alkaloids and 2,5-diketopiperazines. To understand the influence of plant genetics, breeding, and processing on the sensory profile of cocoa products, high-throughput sensometabolite quantitation must be performed throughout all of these steps. In this work, we present a rapid, sensitive, and robust quantitation method on a single ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) platform, requiring minimal workup for any sample type from farm to fork. This method was applied to a global set of 75 cocoa bean samples from all over the world before and after using a uniform roasting protocol. Within this world map, geographical origin did not predetermine cocoa taste profiles, whereas simulated processing by roasting was confirmed to be crucial in profile development. This method will open avenues for further studies to ultimately enable chocolate producers to control and optimize the taste properties of products as well as to monitor raw material selection and processing.Saturated N-heterocycles are prevalent in pharmaceutical and agrochemical industries, yet remain challenging to catalytically alkylate. Most strategies for C-H activation of these challenging substrates use protected amines or high loadings of precious metal catalysts. We report an early transition-metal system for the broad, robust, and direct alkylation of unprotected amine heterocycles with simple alkenes. Short reaction times are achieved using an in situ generated tantalum catalyst that avoids the use of bases, excess substrate, or additives. In most cases, this catalyst system is selective for the branched reaction product, including examples of products that are generated with excellent diastereoselectivity. Alkene electronic properties can be exploited for substrate-modified regioselectivity to access the alternative linear amine alkylation product with a group 5 catalyst. This method allows for the facile isolation of unprotected N-heterocyclic products, as useful substrates for further reactivity.Based on the promising biomedical developments in wound healing strategies, herein, a new nanobiocomposite scaffold was designed and presented by incorporation of carboxymethyl cellulose hydrogels prepared using epichlorohydrin as a cross-linking agent (CMC hydrogel), a natural silk fibroin (SF) protein, and magnesium hydroxide nanoparticles (Mg(OH)2 NPs). Biological evaluation of the CMC hydrogel/SF/Mg(OH)2 nanobiocomposite scaffold was conducted via in vitro cell viability assays and in vivo assays, red blood cell hemolysis, and antibiofilm assays. Considering the cell viability percentage of Hu02 cells (84.5%) in the presence of the prepared nanobiocomposite after 7 days, it was indicated that this new nanoscaffold was biocompatible. The signs of excellent hemocompatibility and the high antibacterial activity were observed due to the low-point hemolytic effect (8.3%) and high-level potential in constraining the P. aeruginosa biofilm formation with a low OD value (0.13). Moreover, in vivo wound healing assay results indicated that the wound healing method was faster in mice treated with the prepared nanobiocomposite scaffold (82.29%) than the control group (75.63%) in 12 days. Apart from the structural characterization of the CMC hydrogel/SF/Mg(OH)2 nanobiocomposite through FTIR, EDX, FESEM, and TG analyses, compressive mechanical tests, contact angle, porosity, and swelling ratio studies indicated that the combination of the CMC hydrogel structure with SF protein and Mg(OH)2 NPs could significantly impact Young’s modulus (from 11.34 to 10.14 MPa), tensile strength (from 299.35 to 250.78 MPa), elongation at break (12.52 to 12.84%), hydrophilicity, and water uptake capacity (92.5%).To explore natural-product-based pesticidal candidates and high value-added application of cholesterol in agriculture, oximinoether derivatives of cholesterol-containing isoxazoline/isoxazole fragments (I-1∼I-16 and II-1∼II-18) were semiprepared by structural optimization of cholesterol. Their structures were characterized by optical rotation, high-resolution mass spectrometry (HRMS), IR, and 1H NMR spectroscopy. Particularly, the Z configurations of oxime fragments at the C-7 position of target compounds were undoubtedly determined by X-ray crystallography. Against Mythimna separata Walker, compounds 3e, I-8, I-14, and II-3 showed 2.4-2.7-fold growth inhibitory activity of the precursor cholesterol. Against Plutella xylostella Linnaeus, compounds I-6, I-7, and I-9 showed 2.4-2.7-fold oral toxicity of cholesterol. Against Aphis citricola Van der Goot, compounds 2e and II-15 exhibited 4.9 and 5.8-fold aphicidal activity of cholesterol, respectively. Notably, they showed good control effects (3.0-5.0-fold promising control efficiency of 1) against A. citricola in the greenhouse. Structure-activity relationships (SARs) suggested that the C-3 hydroxyl group and the C-7 position of cholesterol are two important modification sites. It will pave the way for future structural optimization and application of cholesterol derivatives as potential pesticidal agents in agriculture.Uranyl(VI) complexes with pentadentate N3O2-donating Schiff base ligands having various substituents at the ortho (R1) and/or para (R2) positions on phenolate moieties, R1,R2-Mesaldien2-, were synthesized and thoroughly characterized by 1H nuclear magnetic resonance, infrared, elemental analysis, and single-crystal X-ray diffraction. Molecular structures of UO2(R1,R2-Mesaldien) are more or less affected by the electron-donating or -withdrawing nature of the substituents. The redox behavior of all UO2(R1,R2-Mesaldien) complexes was investigated to understand how substituents introduced onto the ligand affect the redox behavior of these uranyl(VI) complexes. As a result, the redox potentials of UO2(R1,R2-Mesaldien) in dimethyl sulfoxide increased from -1.590 to -1.213 V with an increase in the electron-withdrawing nature of the substituents at the R1 and R2 positions. The spectroelectrochemical measurements and theoretical calculation [density functional theory (DFT) and time-dependent DFT calculations] revealed that the center U6+ of each UO2(R1,R2-Mesaldien) complex undergoes one-electron reduction to afford the corresponding uranyl(V) complex, [UO2(R1,R2-Mesaldien)]-, regardless of the difference in the substituents. Consequently, the redox active center of uranyl(VI) complexes seems not to be governed by the redox potentials but to be determined by whether the LUMO is centered on a U 5f orbital or on one π* orbital of a surrounding ligand.Exploring highly efficient near-infrared (NIR) emitting materials is desirable for the advancement of next-generation smart NIR light sources. Different from most reported Cr3+-doped emitters with far-red emissions, Yb3+-activated phosphors are expected to yield pure NIR (∼1000 nm) light. Herein, a new hot-injection route using all metal-oleate salts to fabricate Yb3+-doped CsPbCl3 perovskite nanocrystals (PeNCs) is reported for the first time, which produce PeNC-sensitized Yb3+ NIR emission with photoluminescence quantum yields (PLQYs) higher than 100%. With the help of temperature-dependent PL spectra, femtosecond transient absorption spectra, and time-resolved PL spectra, it is evidenced that the in situ produced intrinsic shallow trap states in a CsPbCl3 host play a key role in facilitating the picosecond nonradiative cooperative energy transfer from PeNCs to two Yb3+ dopants simultaneously. Using the optimized Yb3+CsPbCl3 quantum cutters, a phosphor-converted NIR light-emitting diode (pc-NIR-LED) is fabricated, exhibiting an external quantum efficiency of 2%@28 mA, a high NIR output irradiance of 112 mW/cm2@400 mA, and excellent long-term stability. Finally, the designed pc-NIR-LED is demonstrated to have great potential as an invisible night-vision light source.Three thiocyanate-free cycloruthenated complexes, DUY24-O, DUY24, and DUY24-Se containing furan, thiophene, and selenophene, respectively, as a part of the cycloruthenated ring, were designed to reveal the function of the chalcogen atom on the physicochemical and photovoltaic performance of the cycloruthenated sensitizers applied in dye-sensitized solar cells (DSCs). The three sensitizers have a similar molecular size; therefore, the effect of molecular dimensions on their photovoltaic performance can be negligible. NMR data, electron-donating resonance effects, optical properties, and the energy levels of the frontier orbitals reveal that the physical/photovoltaic properties of the three sensitizers were affected significantly by the chalcogen atom on the cyclometalated chalcogenophene ring. The λmax (both in ethanol and adsorbed on TiO2), frontier orbital level, and dye loading of thiophene- and selenophene-containing dyes are very close. Nevertheless, DUY24-Se has a higher molar absorption coefficient comp The physicochemical and photovoltaic properties as well as the adsorption behavior of the dye on the TiO2 anode for the cycloruthenated sensitizers affected significantly by the chalcogen atom of the chalcogenophene on the cyclometalated ring provide a new strategy to design high-efficiency NCS-free cyclometalated sensitizers for DSCs.ConspectusThe development of clean energy generation, transmission, and distribution technology, for example, high energy density batteries and high efficiency solar cells, is critical to the progress toward a sustainable future. Such advancement in both scientific understanding and technological innovations entail an atomic- and molecular-resolution understanding of the key materials and fundamental processes governing the operation and failure of the systems. These dynamic processes span multiple length and time scales bridging materials and interfaces involved across the entire device architecture. However, these key components are often highly sensitive to air, moisture, and electron-beam radiation and therefore remain resistant to conventional nanoscale interrogation by electron-optical methods, such as high-resolution (scanning) transmission electron microscopy and spectroscopy.Fortunately, the rapid progress in cryogenic electron microscopy (cryo-EM) for physical sciences starts to offer researchers new tools and methods to probe these otherwise inaccessible length scales of components and phenomena in energy science.