Journal literature is an important source of scientific data. The manual indexing method was used to identify and extract scientific data for long time. With the development of information technology and artificial intelligence methods, it is gradually becoming possible to automatically identify and extract scientific data from journal literature. In this paper, the method of automatic identification and extraction of chemical data from journal articles was studied by language expression patterns and rule-based natural language processing (NLP) technology, and the automatic identification and extraction of 2022 was completed, and more than 30 kinds of chemical data including product characteristics, synthetic reaction parameters, physical property data, and spectral data were extracted. After data extraction, the corresponding databases have been built, and the knowledge service of the Chinese Journal of Organic Chemistry has been provided. A performance test of all 422 articles in the Journal of Organic Chemistry in 2022 showed that the accuracy of optical rotation data identification and extraction was 100%, melting point data was 99.85%, fluorine nuclear magnetic spectroscopy was 99.55%, carbon nuclear magnetic spec-troscopy was 99.80%, material form data was 99.47%, and product name was 98.76% (a total of 4665 product names were extracted, of which 58 were problematic product names). The current method to identify product name uses irrelevant content exclusion method based on local scenes, and the accuracy of product name recognition is expected to be improved if an identification method of system and semi-system nomenclature is used. Logically, the automatic identification and extraction method based on language expression patterns and natural language processing technology is not limited by disciplines and is suitable for all scientific data.

Paxdaphnine A (1) and daphlongamine B (2) are two heptacyclic Daphniphyllum alkaloids, each containing eight consecutive stereogenic centers. We achieved the first synthesis of these molecules in racemic form by using a biomimetic aza-Prins cyclization strategy. Paxdaphnine B (3), a putative biogenetic precursor of 1 and 2, was also obtained in the synthesis. A pentacyclic analogue of 3 was prepared in a scalable manner and served as a common intermediate. The sterically congested cyclopentane moiety of this intermediate was constructed via a nitrone-olefin cycloaddition reaction, and the assembly of its diquinane motif relied on an intramolecular Pauson-Khand reaction. Despite the unsatisfactory outcome of the initial biomimetic aza-Prins reaction of 3 with HCHO, we utilized the N-cyanomethyl derivative of 3 as an alternative substrate in combination with AgTFA as a promoter to rescue the biomimetic route to 1. On the basis of a similar strategy, an aza-Prins cyclization-lactonization cascade, involving a different terminating nucleophile, was developed for the synthesis of 2.

The simultaneous chain-growth and step-growth polymerization of p-methoxystyrene was achieved using rare-earth metal complexes (Sc, Y, Gd to Lu) based on an octahydrofluorenyl ligand. As the ionic radius of the metal increased (except for Sc), the polymerization activity of the rare-earth metal catalyst also increased, with a significant difference in the observed rate constants (kobs = 9.03 x 10-5 to 1.64 x 10-2 min-1). In the early stages of polymerization, catalysts with smaller metal ions preferentially formed C-H polyaddition sequences and suppressed the continuous insertion of double bonds in the monomer more effectively. A detailed investigation revealed that the efficient formation of a continuous C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 C bond insertion sequence through the chain-growth pathway, which is strongly correlated with the ionic radii of rare-earth metal catalysts, significantly influenced the acceleration of polymerization activity. Density functional theory (DFT) calculations indicated that the CC insertion reaction was more kinetically favorable than C-H activation in the initial monomer reaction. Moreover, as the radius of the metal ionic center decreases, the probability of C-H activation increases markedly in the following monomer insertion.

In response to the growing demand for sustainable and efficient self-emulsifying systems, this study presents a novel strategy for the development of naturally derived self-emulsifying agents via functional group deprotection. Cholic acid was chemically modified by temporarily masking its hydroxyl and carboxyl groups with ethyl vinyl ether, yielding a lipophilic cholic acid (LCA) intermediate with controlled structural stability. Upon exposure to aqueous or biological environments, LCA undergoes hydrolytic deprotection, regenerating amphiphilic cholic derivatives that exhibit excellent self-emulsifying performance and tunable functional properties. Furthermore, LCA displays high oil solubility, enabling effective solubilization and dispersion of poorly water-soluble drugs as well as quantum dots. This work provides a versatile and energy-efficient platform for the design of natural self-emulsifying agents with potential applications in drug delivery and advanced functional materials.

Nucleotide-containing metabolites, e.g., NAD, can serve as noncanonical initiating nucleotides (NCIN) during transcription, yielding NCIN-capped RNAs (NCIN-RNAs). Current profiling strategies are limited to detecting specific metabolite caps and lack an epitranscriptome-wide approach for quantifying the ratio between NCIN- and m7G-capped forms. Here, we develop the CompasSeq analytical platform, which integrates experimental and computational frameworks, enabling comprehensive and quantitative assessment of NCIN-RNAs at the transcript resolution. CompasSeq utilizes carefully devised enzymatic reactions to selectively capture NCIN-RNAs. By introducing proper spike-ins, CompasSeq can analyze the stoichiometry of NCIN caps. We further design an orthogonal method, the quantitative exoribonuclease reduction assay, to validate newly identified NCIN-RNAs and their capping ratios. Using CompasSeq, we quantify previously unexplored NCIN capping percentages from mouse liver and illustrate their age-associated dynamics. Moreover, we uncover a dichotomy between RNA expression and NCIN capping in genes impinging on age-related pathways. Our study presents both experimental and computational solutions for in-depth analysis of NCIN-RNAs, paving the road for functional investigations into NCIN-RNAs.

Fluoropolymers can be utilized as dielectric substrates to ensure signal transmission speed and quality in modern communication technology. However, conventional fluoropolymer materials such as polytetrafluoroethylene (PTFE) are constrained by limited thermal stability and inferior processability. In this paper, two monomers (DBA-FBCB and DBAF-FBCB) based on benzocyclobutene and fluorobenzene groups have been successfully synthesized via effective C-H bond activation and nucleophilic aromatic substitution reactions. The monomers were thermally cross-linked to fluoropolymers (p-DBA-FBCB and p-DBAF-FBCB). Those polymers exhibited superior thermal stability with a glass transition temperature (T-g) > 370 degrees C, a 5% weight loss temperature (T-5d) higher than 430 degrees C, and low coefficient of thermal expansion (CTE) of 60.9 ppm degrees C-1 from 35 degrees C to 250 degrees C. p-DBAF-FBCB displayed excellent dielectric properties with a low dielectric constant (D-k) of 2.51 and dielectric loss factor (tan delta) of 2.41 x 10(-3) at a high frequency of 5 GHz, as well as an average D-k of 2.45 with an average tan delta of 1.5 x 10(-3) at the frequency from 1 to 10 MHz. The results demonstrate that these fluoropolymers are promising candidates for low-dielectric substrates or packaging materials in high-frequency communications or microelectronics industries.

Selenoproteins, defined as proteins containing the 21st amino acid, selenocysteine (Sec, U), are functionally important but rare, with only 25 selenoproteins characterized in the entire human proteome to date. To comprehensively analyze selenoproteomes, previously developed selenocysteine-specific mass spectrometry (SecMS) and the selenocysteine insertion sequence (SECIS)-independent selenoprotein database (SIS) have provided effective tools for analyzing the selenoproteome and, more importantly, hold the potential to uncover new selenoproteins. In this study, a deep learning approach is employed to develop the DeepSecMS method. Given the rarity of Sec and its chemical similarity to cysteine (Cys, C), a proxy training strategy is utilized using a large dataset of Cys-containing peptides to generate a large-scale theoretical library of Sec-containing peptides. It is shown that DeepSecMS enables the accurate prediction of critical features of Sec-containing peptides, including MS2, retention time (RT), and ion mobility (IM). By integrating DeepSecMS with data-independent acquisition (DIA) methods, the identification of known selenoproteins is significantly enhanced across diverse cell types and tissues. More importantly, it facilitates the identification of numerous highly scored, potential novel selenoproteins. These findings highlight the powerful potential of DeepSecMS in advancing selenoprotein research. Moreover, the proxy training strategy may be extended to the analysis of other rare post-translational modifications.

Bioisosteric replacement of ketones with three-dimensional (3D) motifs, such as oxetanes and azetidines, has emerged as a powerful tool in molecular design, enabling access to novel chemical space with improved pharmacokinetic profiles. However, general methods for the asymmetric synthesis of stereocenters adjacent to these strained, 3D frameworks remain scarce. Here, we report a nickel-catalyzed, enantioselective reductive cross-coupling between aldehydes and four-membered heterocyclic alkenes to construct alpha-hydroxy ketones bioisosteres with high efficiency and selectivity. Guided by N-heterocyclic carbene (NHC) ligands, the reaction proceeds with broad functional group tolerance, affording enantioenriched products in yields of up to 94% and an enantiomeric ratio (e.r.) of 99.8:0.2. The protocol is particularly amenable to the synthesis of enantioenriched alpha-hydroxy difluoromethylene alkanes. Mechanistic investigations revealed how strain-enabled reactivity and ligand control govern chemo-, regio-, and stereoselectivity. The synthetic utility of the method is demonstrated through gram-scale preparation and diverse downstream derivatizations, offering a versatile platform for accessing previously elusive classes of stereodefined bioisosteres.

A primary challenge in defluorinative functionalization of readily accessible trifluoromethyl reagents is exhaustive defluorination caused via repetition of the same reaction where the C-F bond strength decreases sequentially during defluorination. In this work, we introduced a novel comovement group (CG) strategy where the cleavage of each C-F bond occurs through different reactions initiated by distinct CGs, rather than by direct activation of the C-F bond, thus enabling an orderly and diversified triple C-F bond functionalization reaction. The reaction provides straightforward access to a wide range of alpha-ketoamides and quinoxalinones from readily available trifluoromethyl diazo compounds and amines under mild conditions using water and oxygen in air as oxygen atom sources. This method features high bond formation efficiency (two C 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 O bonds and one C-N bond in one-pot), exceptionally high regio- and chemoselectivities, and broad functional group compatibility, including alkyl and aryl amines, amino acids, peptides, and drug-like molecules. The emergent principle outlined herein provides guidelines to inspire further research endeavors in fluorine chemistry with both exceptional precision and generality.

The radical migration (RaM) mechanism via photoinduced transformation is a powerful tool in organic synthesis to construct new molecular scaffolds. Herein we disclose a metal-free, photoinduced 1,2-carbonyl migration of beta,gamma-unsaturated ketones to afford a wide range of valuable beta-SF5/beta-CF3SF4 ketones. This transformation exhibits broad functional group tolerance and is suitable for the late-stage modification of complex molecules in up to 93% yield with excellent chemoselectivity and regioselectivity. Furthermore, mechanistic studies reveal that the selective synthesis of 1,3-chloropentafluorosulfanylation can be accomplished via a carbonyl migration followed by a radical chain propagation pathway. Finally, SF5-containing compound 5 exhibits potential anticancer activity, underscoring the utility of this approach.

Regulating through-space interactions offers a promising strategy for designing multifunctional luminescent materials. However, integrating stimuli-responsive photophysical behaviors into such systems remains challenging. In this study, a series of carbene-metal-amide bimetallic Au(I) complexes featuring dynamic through-space interactions is reported that enable aggregation-induced emission and full-color-tunable photoactivated phosphorescence. Single-crystal X-ray diffraction combined with theoretical calculations reveals conformationally adaptive frameworks that facilitate ligand rotational freedom (carbazole) and N-heterocyclic carbene conformational flexibility, enabling precise modulation of intramolecular through-space interactions. These complexes exhibit multi-stimuli-responsive phosphorescence, allowing reversible, on-demand switching of emission color and intensity across molecular and macroscopic scales. By strategically blending phosphors, white-light emission with a CIE 1931 coordinate of (0.30, 0.31) is achieved. The materials further demonstrate time-resolved information encryption capabilities, making them ideal for light-activated printing and high-security anti-counterfeiting inks. This work advances the rational design of smart luminescent platforms for applications in optoelectronics, sensing, and photonic security.