Differentiating between Acidic and Basic Surface Hydroxyls on Metal Oxides by Fluoride Substitution: A Case Study on Blue TiO2 from Laser Defect Engineering

Both oxygen vacancies and surface hydroxyls play a crucial role in catalysis. Yet, their relationship is not often explored. Herein, we prepare two series of TiO₂ (rutile and P25) with increasing oxygen deficiency and Ti³⁺ concentration by pulsed laser defect engineering in liquid (PUDEL), and selectively quantify the acidic and basic surface OH by fluoride substitution. As indicated by EPR spectroscopy, the laser-generated Ti³⁺ exist near the surface of rutile, but appear to be deeper in the bulk for P25. Fluoride substitution shows that extra acidic bridging OH are selectively created on rutile, while the surface OH density remains constant for P25. These observations suggest near-surface Ti³⁺ are highly related to surface bridging OH, presumably the former increasing the electron density of the bridging oxygen to form more of the latter. We anticipate that fluoride substitution will enable better characterization of surface OH and its correlation with defects in metal oxides.     

Pore-Environment-Dependent Photoresponsive Oxidase-Like Activity in Hydrogen-Bonded Organic Frameworks

Mimicking the bioactivity of native enzymes through synthetic chemistry is an efficient means to advance the biocatalysts in a cell-free environment, however, remains long-standing challenges. Herein, we utilize structurally explicit hydrogen-bonded organic frameworks (HOFs) to mimic photo-responsive oxidase, and uncover the important role of pore environments on mediating oxidase-like activity by means of constructing isostructural HOFs. We discover that the HOF pore with suitable geometry can stabilize and spatially organize the catalytic substrate into a favorable catalytic route, as with the function of the native enzyme pocket. Based on the desirable photo-responsive oxidase-like activity, a visual and sensitive HOFs biosensor is established for the detection of phosphatase, an important biomarker of skeletal and hepatobiliary diseases. This work demonstrates that the pore environments significantly influence the nanozymes’ activity in addition to the active center.     

[2+2+1+1] Cycloaddition for de novo Synthesis of Densely Functionalized Phenols

A unique benzannulation strategy for regioselective de novo synthesis of densely functionalized phenols is described. Through metal-mediated formal [2+2+1+1] cycloaddition of two different alkynes and two molecules of CO, a series of densely functionalized phenols were obtained. The benzannulation strategy allows efficient regioselective installation up to five different substituents on a phenol ring. The resulting phenols have a substitution pattern different from those obtained from Dötz and Danheiser benzannulations.     

Bis-peri-dinaphtho-rylenes: Facile Synthesis via Radical-Mediated Coupling Reactions and their Distinctive Electronic Structures

Polycyclic aromatic hydrocarbons (PAHs) with a one-dimensional (1D), ribbon-like structure have the potential to serve as both model compounds for corresponding graphene nanoribbons (GNRs) and as materials for optoelectronics applications. However, synthesizing molecules of this type with extended π-conjugation presents a significant challenge. In this study, we present a straightforward synthetic method for a series of bis-peri-dinaphtho-rylene molecules, wherein the peri-positions of perylene, quaterrylene, and hexarylene are fused with naphtho-units. These molecules were efficiently synthesized primarily through intramolecular or intermolecular radical coupling of in situ generated organic radical species. Their structures were confirmed using X-ray crystallographic analysis, which also revealed a slightly bent geometry due to the incorporation of a cyclopentadiene ring at the bay regions of the rylene backbones. Bond lengh analysis and theoretical calculations indicate that their electronic structures resemble pyrenacenes more than quinoidal rylenes. That is, the aromatic sextets are predominantly localized along the long axis of the skeletones. As the chain length increases, these molecules exhibit enhanced electronic absorption with a bathochromic shift, and multiple amphoteric redox waves. This study introduces a novel synthetic approach for generating 1D extended PAHs and GNRs, along with their structure-dependent electronic properties.     

Balancing the Crystallinity and Film Formation of Metal–Organic Framework Membranes through In Situ Modulation for Efficient Gas Separation

Polycrystalline metal–organic framework (MOF) layers hold great promise as molecular sieve membranes for efficient gas separation. Nevertheless, the high crystallinity tends to cause inter-crystalline defects/cracks in the nearby crystals, which makes crystalline porous materials face a great challenge in the fabrication of defect-free membranes. Herein, for the first time, we demonstrate the balance between crystallinity and film formation of MOF membrane through a facile in situ modulation strategy. Monocarboxylic acid was introduced as a modulator to regulate the crystallinity via competitive complexation and thus concomitantly control the film-forming state during membrane growth. Through adjusting the ratio of modulator acid/linker acid, an appropriate balance between this structural “trade-off” was achieved. The resulting MOF membrane with moderate crystallinity and coherent morphology exhibits molecular sieving for H₂/CO₂ separation with selectivity up to 82.5.     

Cu-Doped MoSi2N4 Monolayer as a Potential NH3 Sensor

Cu doped MoSi₂N₄ monolayer (Cu-MoSi₂N₄) was firstly proposed to analyze adsorption performances of common gas molecules including O₂, N₂, CO, NO, NO₂, CO₂, SO₂, H₂O, NH₃ and CH₄ via density functional theory (DFT) combining with non-equilibrium Green's function (NEGF). The electronic transport calculations indicate that Cu-MoSi₂N₄ monolayer has high sensitivity for CO, NO, NO₂ and NH₃ molecules. However, only NH₃ molecule adsorbs on the Cu-MoSi₂N₄ monolayer with moderate strength (−0.55 eV) and desorbs at room temperature (2.36×10⁻³ s). Thus, Cu-MoSi₂N₄ monolayer is demonstrated as a potential NH₃ sensor.     

High-performance liquid chromatography micro-fraction bioactive evaluation combined with countercurrent chromatographic separation of antioxidants from Citrus peel and their tyrosinase inhibition activities

In the present study, high-performance liquid chromatography micro-fraction bioactive evaluation and high speed countercurrent chromatography were performed on screening, identification and isolation of antioxidants from Citrus peel. Three compounds were screened as antioxidants and tyrosinase inhibitors using 2,2′-azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid) radical cation scavenging assay and tyrosinase activity test, then they were identified as eriocitrin, narirutin and hesperidin. Moreover, the solvent system ethyl acetate-n-butanol-water (6:4:10, v/v/v) was used for separation of ethyl acetate extract of Citrus peel by high speed countercurrent chromatography. In total, 0.45 mg of eriocitrin with 87.10% purity, 2.04 mg of narirutin with 95.19% purity and 1.35 mg of hesperidin with 95.19% purity were obtained from 20 mg of ethyl acetate extract of Citrus peel in a single run and then each component was subjected to 2,2′-azino-bis (3-ethyl-benzothiazoline-6-sulfonic acid) radical cation scavenging assay and tyrosinase inhibition assay. Eriocitrin showed great antioxidant activity (the half-maximum concentration: 3.65 µM) and tyrosinase inhibition activity (the half-maximum concentration: 115.67 µM), while narirutin and hesperidin exhibited moderate activity. Tyrosinase inhibition activity for eriocitrin in vitro was reported for the first time. Furthermore, molecular docking between eriocitrin and mushroom tyrosinase was also studied.     

Miniaturized matrix solid-phase dispersion and solid-phase clear-up combined with capillary electrophoresis for efficient determination of trace bioactive components in complicated sample matrix: Take Wubi Shanyao Pill as an example

Accurate quantitative analysis of trace analytes in a complicated matrix is a challenge in modern analytical chemistry. An appropriate analytical method is considered to be one of the most common gaps during the whole process. In this study, a green and efficient strategy based on miniaturized matrix solid-phase dispersion and solid-phase extraction combined with capillary electrophoresis was first proposed for extracting, purifying and determining target analytes from complicated matrix, using Wubi Shanyao Pill as an example. In detail, 60 mg of samples were dispersed on MCM-48 to obtain high yields of analytes, then the extract was purified with a solid-phase extraction cartridge. Finally, four analytes in the purified sample solution were determined by capillary electrophoresis. The parameters affecting the extraction efficiency of matrix solid-phase dispersion, purification efficiency of solid-phase extraction and separation effect of capillary electrophoresis were investigated. Under the optimized conditions, all analytes demonstrated satisfactory linearity (R²>0.9983). What's more, the superior green potential of the developed method for the determination of complex samples was confirmed by the Analytical GREEnness Metric Approach. The established method was successfully applied in the accurate determination of target analytes in Wubi Shanyao Pill and thus provided reliable, sensitive, and efficient strategy support for its quality control.     

Development of a general separation strategy by countercurrent chromatography using sanshools from Zanthoxylum bungeanum oleoresin as a case study

Three kinds of sanshools were separated from Zanthoxylum bungeanum oleoresin by high-speed countercurrent chromatography. Sanshools are a series of amide compounds extracted from the Zanthoxylum bungeanum. Due to similar structures, polarities, and dissociation constants, it was challenging to select an appropriate solvent system for their complete separation by countercurrent chromatography. To address this challenge, a solvent-system-selection strategy was proposed to identify a relatively suitable solvent system. Additionally, a separation procedure incorporating multi-elution modes selection was established to separate similar compounds in a logical order. Ultimately, a solvent system comprising n-hexane:ethyl acetate:methanol:water in a ratio of 19:1:1:5.67 was selected. Three amide compounds with high purity were obtained through the use of recycling elution mode to improve separation resolution: hydroxy-ε-sanshool (8.4 mg; purity: 90.64%), hydroxy-α-sanshool (326.4 mg; purity: 98.96%), and hydroxy-β-sanshool (71.8 mg; purity: 98.26%) were obtained from 600 mg sanshool crude extract. The summarized solvent-system-selection strategy and separation procedure incorporating multi-elution modes may instruct countercurrent chromatography users, particularly novices, seeking to separate compounds with highly similar chemical properties.     

Facile synthesis of spherical covalent organic frameworks for enrichment and quantification of aryl organophosphate esters in mouse serum and tissues

Here, an imine-linked-based spherical covalent organic framework (COF) was prepared at room temperature. The as-synthesized spherical COF served as an adsorbent in dispersive solid-phase extraction (dSPE), by its virtue of great surface area (1542.68 m²/g), regular distribution of pore size (2.95 nm), and excellent stability. Therefore, a simple and high-efficiency dispersive solid phase extraction method based on a spherical COF coupled with high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was established to determine aryl organophosphate esters in biological samples. This approach displayed favorable linearity in the range of 10.0–1000.0 ng/L (r > 0.9989), a high signal enhancement factor (58.8–181.8 folds) with low limits of detection (0.3–3.3 ng/L). Moreover, it could effectively eliminate complex matrix interference to accurately extract seven aryl organophosphate esters from mouse serum and tissue samples with spiked recoveries of 82.0%–117.4%. The as-synthesized spherical COF has been successfully applied in sample preparation. The dSPE-HPLC-MS/MS method based on a spherical COF has potential application to study the pollutants' metabolism in vivo.