Monthly ,Founded in 1964 Resume Publication in 1980 Editor-in-Chief:YU Jihong ISSN 0251-0790 CN 22-1131/O6
Heparin(HP) and heparan sulfate(HS) are highly anionic glycosaminoglycans that play essential roles in diverse biological processes through the metal ion-mediated interactions with proteins. However, direct characterization of HS-metal ion interactions at the single-molecule level in solution remains challenging. Nanopore electrochemistry is a label-free and single-molecule technique that enables direct analysis of individual molecular interactions. In this study, a T232K/K238Q Aerolysin nanopore featuring an enhanced electrostatic repelling barrier was utilized to probe the interactions between HS and different metal ions. By systematically varying the electrolyte cations(Na+, K+, and Ca2+), we have found that the metal ions significantly regulate HS translocation behavior by modulating its conformation, charge screening, and HS-nanopore interactions. Notably, in addition to Ca2+, which exhibits strong binding affinity to HS, the monovalent cations Na⁺ and K⁺ with similar physicochemical properties and weaker binding also induce distinct single-molecule signal signatures. Our results demonstrate that the nanopore-based single-molecule analysis holds strong potential to resolve the fine structural features of HS, enabling the characterization of sulfation site distributions, repeat-unit lengths, and related sequence features, and thereby providing a new avenue for high-resolution analysis of complex glycans.
Two zinc-based complexes, [Zn(4,4′-bipy)(H₂O)₄]·(4-ABS)₂(1, CCDC: 2171834) and [Zn(4,4′- bipy)(H₂O)₄]·(4-MBS)₂(2, CCDC: 2225758), were obtained through solvothermal synthesis with Zn(II) salts using p-aminobenzenesulfonate(4-ABS-) and p-methylbenzenesulfonate(4-MBS-) as the main ligands and 4,4′- bipyridine(4,4′-bipy) as the auxiliary ligand. The complexes were characterized by single-crystal X-ray diffraction(SXRD), infrared spectroscopy(IR), thermogravimetric analysis(TGA), powder X-ray diffraction(PXRD), nitrogen adsorption-desorption test and field-emission scanning electron microscopy(SEM). The performance of complexes 1 and 2 in catalyzing the synthesis of 2,3-diphenyl-2,3-dihydroquinazoline-4(1H)-one was investigated, and complex 1 with better catalytic effect was chosen for substrates universality experiments. The experimental results showed that high-yield products could be obtained using a small amount of catalyst in short time under solvent-free conditions. This green process was applicable to a variety of raw materials amines/ammonium compounds and aromatic aldehydes with different substituents. In addition, density functional theory(DFT) was used to optimize the structures of complex 1 and the three reactants. Through computational analysis of the frontier molecular orbitals(FMO), the reaction sequence and the core active sites of complex 1 for the three reactants were inferred. The active sites of complex 1 and the reaction sites of the reaction substrates were further predicted in detail by analyzing the electrostatic potential(ESP) of the molecular surface, the average local ionization energy(ALIE) and the Mulliken charges. Finally, the reaction mechanism of multi-site synergistic catalysis of the complexes was explained in combination with DFT.
A method of hydrothermal synthesis coupled with activation etching was employed to synthesize zinc oxide(ZnO) particles with six distinct morphologies: rod, tube, screw, rod-flower, tube-flower, and screw-flower. The controlled synthesis of ZnO from dispersed rods to aggregated rod-flower clusters was achieved by adjusting the parameters of the hydrothermal reaction. Moreover, by exploiting the differences in the stability of various crystal faces, a customized post-etching method was used to effectively control the morphological evolution of ZnO from rod-like structure to tubular and screw-like structures. The results of photoelectrochemical test indicated that the distinct morphology of ZnO played a significant role in its photoelectrochemical property. These findings offer valuable insights into the synthesis of ZnO with specific morphologies to tailor its properties for particular application.
Fe-N-CDs nanopaticles were successfully prepared by one-step hydrothermal method using L-histidine and Fersulfate heptahydrate(FeSO₄·7H₂O) as precursors. The introduction of Fe atoms produced more active sites on the surface of carbon dots, promoted the electron transfer in the catalytic process, and thus improved the catalytic efficiency of the material. The Fe-N-CDs nanopaticles effectively catalyzed the decomposition of hydrogen peroxide (H2O2) to generate hydroxyl radicals(•OH), which subsequently oxidized 3,3',5,5'-tetramethylbenzidine(TMB) to form a blue oxidation product(oxTMB) with a characteristic absorption peak at 652 nm. Curcumin, a natural polyphenolic compound widely found in plants, exhibits excellent antioxidant properties and antidepressant effects. Leveraging the ability of curcumin to reduce oxTMB and cause its color to fade, a quantitative relationship between the change in absorbance and the curcumin content was established. This enabled the development of a colorimetric sensing method for the detection of curcumin. The experimental results demonstrated that this method possesses good selectivity, anti-interference capability and rapid response characteristics. It can be applied for the colorimetric analysis of antioxidant components in pharmaceuticals and food products, offering a new analytical approach for quality assessment of related products and the development of antidepressant drugs.
Amino acids(both L- and D-enantiomers) serve as crucial biomarkers for indicating the sources of organic matter and diagenetic processes within marine sedimentary environments. Consequently, developing methods for their precise detection in marine sediments is of significant importance. This study established a novel method for the simultaneous determination of 17 L-amino acids and 7 D-amino acids in marine sediments using online solid-phase extraction(SPE) coupled with liquid chromatography-time-of-flight mass spectrometry(LC-TOF/MS). A C18 guard column served as the online SPE column, while an ultra-high-performance reversed-phase C18 analytical column (1.8 μm particle size) was employed for separation. Utilizing dual acidic and alkaline mobile phase systems, efficient separation of various L- and D-amino acids was achieved. Detection was performed online using high- resolution electrospray ionization TOF/MS in full scan mode. The results demonstrate that accurate quantification of various L- and D-amino acids can be achieved by direct injection analysis using online SPE-LC-TOF/MS following hydrochloric acid hydrolysis of marine sediment samples, 5-fold dilution, and derivatization. The spiked recoveries for the various amino acids ranged from 66.1% to 106.8%, with relative standard deviations(RSD) between 2.40% and 12.3%. The method exhibited wide linear ranges, and all correlation coefficients(R²) were greater than 0.990. Compared to conventional liquid chromatography methods, this approach requires only a small sediment sample amount(0.01—0.10 g), making it an effective method for detecting chiral amino acid biomarkers in deep-sea and oceanic hydrothermal vent sediments. Applying this method to analyze L- and D-amino acids in surface sediments from the Western Indian Ocean revealed the presence of all 17 L-amino acids and 7 D-amino acids in all samples, with total concentrations ranging from 1.69 to 19.30 μmol/g(dry weight). Furthermore, the analysis indicated that submarine hydrothermal activity significantly influences the cycling of organic carbon and nitrogen in the deep-sea sedimentary environment.
Using the preclinical drug CVL-231 as a lead compound and introducing the 2-trifluoromethylpyridine moiety from the high-activity compound VU6000918, 27 novel 2-trifluoromethylpyridine cyclobutylamide derivatives were designed and synthesized by modifying the heterocyclic moiety. The allosteric modulatory activity of the compounds on M4 receptor cells was assessed using the FLIPR fluorescence detection technique. The results revealed that several compounds exhibited significant cellular activity, especially for compounds Ⅳ1, Ⅳ12, Ⅳ20, Ⅳ23, Ⅳ25, Ⅳ26, and Ⅳ27. The results of the EC50 determination indicated that compound Ⅳ23 had an EC50 value as low as 979 nmol/L, which is slightly higher than that of the positive control VU0467154. Structure-activity relationship (SAR) analysis revealed that the introduction of a quinoline ring, particularly the 4-methylquinoline moiety, significantly enhanced the activity of the compounds. Molecular-docking simulations revealed that compound Ⅳ23 forms both hydrogen-bond and π-π stacking interactions with the M4 receptor protein(7TRP), providing a plausible mechanistic for its recognition by the target protein. In summary, compound IV23, as a promising lead compound for M4 positive allosteric modulators, provides an important research basis for subsequent structural optimization and drug development.
Using triphenylmethyl(Trt) and acetaminomethyl(Acm) as the protective groups of the cysteine thiol side chain, and H2O2 and I2 as oxidants, respectively, through the optimization of reaction conditions, the "one-pot" step-by-step precise synthesis of polypeptide compounds containing two pairs of disulfide bonds was achieved. This reaction strategy does not require purification of the intermediate products, is easy to operate, and has a fast reaction rate. The two pairs of disulfide bonds in the polypeptide were completely constructed within 20 minutes. The research results show that this reaction strategy has wide substrate applicability. A series of biologically active peptide compounds, including those containing tryptophan and methionine, was obtained by adopting this strategy with high overall yields.
Anisotropic spindle-shaped silica colloidal particles(SSCPs) with tunable geometrical parameters and sizes were synthesized via a segmented, temperature-controlled microemulsion method. Scanning electron microscopy(SEM) characterization results showed that the SSCPs possess a uniform spindle-like morphology with a thicker middle segment and two thinner ends. Using these SSCPs as building blocks, colloidal liquid crystals were assembled driven by shape entropy via gravity sedimentation in a capillary. The resulting structures included smectic, nematic, and isotropic phases. A phase diagram was constructed with the total length(L) of SSCPs as the horizontal axis and the end-to-center diameter ratio(De/Dc) as the vertical axis. When L>1.31 μm and De/Dc<0.72, the formation of the smectic phase was effectively suppressed, and the nematic phase was preferentially induced.
In this article, the electrolytes of mixed solvents for the hard carbon(HC) negative of sodium-ion batteries were designed, using sodium hexafluorophosphate(NaPF6) as the sodium salt and adding propylene carbonate(PC) and dimethyl carbonate(DMC) in an ethylene carbonate(EC) based solvent. The effect and mechanism of different solvent synergistic combinations on the electrochemical performance of HC negative were explored. The sodium solvation structure and the diffusion coefficient of sodium ions in the electrolyte were analyzed by molecular dynamics simulation(MD). The electrochemical performance of HC negative electrode in EC based electrolyte was compared and analyzed through conductivity tests, charge-discharge tests, cycling performance tests, and rate capability tests. The kinetic behavior of sodium ions storage was also analyzed by cyclic voltammetry(CV), galvanostatic intermittent titration technique(GITT), and electrochemical impedance spectroscopy(EIS). The surface morphology and composition of HC anodes before and after cycling were made by scanning electron microscopy(SEM), transmission electron microscopy(TEM), and X-ray photoelectron spectroscopy(XPS), and so on. As a result, the synergistic effect of DMC and PC can significantly improve the ionic conductivity of the electrolyte and diffusion coefficient of sodium ions in electrolyte, optimize the solvation structure, reduce organic by-products and increase anion coordination, promote the generation of inorganic substances in the solid electrolyte interface(SEI) film, effectively reduce the SEI film impedance and charge transfer impedance, and improve the diffusion coefficient of sodium ions in HC. Therefore, the HC anode achieves 362.0 mA·h/g initial capacity, in the 1 mol/L NaPF6-EC/PC/DMC electrolyte at 50 mA/g, and the capacity decays to 353.4 mA·h/g with a capacity retention rate of 97.6% after 50 cycles demonstrating superior rate capability and cycling performance. Thereby, EC/PC/DMC mixed solvents are one of the most promising solvents for the HC anode of sodium ion batteries.
Using the density functional theory(DFT), the comprehensive and in-depth exploration was conducted into the structure, electronic properties, CO adsorption and activation performance of Fe atoms modulated by graphene confinement to reveal the influence of different coordination environment of Fe active centers on Fischer-Tropsch(FT) performance. The binding energies of Fe-doped single-atom defect graphene(FeC@graphene) and Fe-doped di-atom defect graphene are -7.49 and -6.50 eV, respectively, which indicates that FeC@graphene structure exhibits greater stability compared to the Fe2C@graphene. The density of states(DOS) of FeC@graphene exhibits the more significant left-shift compared to that of Fe2C@graphene, with values of 1.5 and 0.8 eV, respectively. The greater left-shift indicates that the FeC@graphene structure possesses lower energy, and the higher stability. The adsorption energies of CO on FeC@graphene and Fe2C@graphene are -1.43 and -1.69 eV, respectively, which reflects that CO adsorption on Fe2C@graphene is more stable than that of FeC@graphene. The d band center values of FeC@graphene and Fe2C@graphene are -1.26 and -0.83 eV, respectively, while their energy band gaps are 0.45 and 0.01 eV, respectively. The closer the d-band center is to the Fermi level, and the smaller the band gap, which is more conducive to the adsorption of species. Thus, compared with FeC@graphene, CO has a higher propensity to be adsorbed onto Fe2C@graphene. The band gap of Fe2C@graphene-CO increases by 0.25 eV, while FeC@graphene decreases by 0.04 eV; the antibonding component of FeC@graphene-CO is more than that of Fe2C@graphene-CO, and the integrated crystal orbital Hamilton population(ICOHP) values are -1.99 and -2.50 eV. These suggest that the interaction between Fe2C@graphene and CO is stronger, while strong interaction is unfavorable for CO activation. On the FeC@graphene and Fe2C@graphene, the most favorable pathway for CO activation follows the sequence: CO* → CHO* → CH* + O*, with an effective energy barrier of 2.53 and 3.50 eV, respectively. It is easier for CO activation on FeC@graphene. Therefore, the three-coordination structure of the active center Fe is more stable and beneficial for enhancing FTS activity.
In this work, a series of CN-B@M2 catalysts composed of B and bimetallic atoms with nitrogen reduction reaction(NRR) activity were screened by high-throughput density functional calculations. CN-B@Fe2, CN-B@Tc2, CN-B@Os2, and CN-B@Re2 were considered as catalysts with good selectivity and NRR activity, with the limiting potentials(UL) of -0.24, -0.34, -0.31 and -0.38 V, respectively. Calculation results show that the adsorption configuration of N2 at B@M2 shows a periodic evolution, and adsorption configuration and energy are regulated by d-band center. UL shows a volcanic distribution with adsorbed N2 charge. B@M2 catalyst with moderate electron donor capacity shows excellent NRR activity. Descriptor Φ used to describe electron donating ability is constructed by quantifying atom electronic properties and topology structure of catalysts. Φ shows a strong linear correlation with adsorption energy, and describes limiting potential of NRR by volcano diagram. Φ and intrinsic properties of catalyst are used as features to predict the adsorption energy and UL. Gradient boosting regression(GBR) is considered the most appropriate method for building a machine learning prediction model due to an R2 of 0.99. This work provides novel insights into the design of rational and efficient NRR catalysts and construction of their descriptors.
Density functional theory(DFT) and time-dependent density functional theory(TD-DFT) methods at the M06-2X/def2-TZVP level were used to systematically reveal the regulatory mechanism of N-1 substituents on the photophysical properties and photocycloaddition reactions of ethyl 1,4-dihydropyridine-3,5-dicarboxylate derivatives(1a—1h). The results demonstrate that the type of N-1 substituent significantly influences the molecular excitation characteristics. Electronic excitations are predominantly characterized by π→π* transitions within the 1,4-dihydropyridine ring. The excited-state charge distribution is highly overlapping and localized in the C=C double bond region of the ring, exhibiting typical localized excitation features. This promotes a nearly planar molecular conformation in the excited state, accompanied by significant bond length changes at key reactive sites, both of which facilitate the occurrence of photocycloaddition reactions. This work establishes a systematic theoretical correlation between the photophysical properties and photocycloaddition reactivity of 1,4-dihydropyridine derivatives, providing important theoretical insights and innovative guidance for designing efficient photochemical eaction systems and constructing polycyclic frameworks.
Bimetallic metal-organic frameworks(MOFs) possess tunable skeletal structures and synergistic effects between multiple metals, demonstrating significant application potential in the field of catalysis. In this study, Cu2+ and Co2+, which have similar electronic structures and ionic radii, were selected as metal centers to successfully construct a bimetallic CuCo-MOF catalyst, achieving efficient and mild air-mediated epoxidation of cycloalkenes without the addition of external initiators or co-reductants. The Cu0.1Co-MOF-BTC-S-150-24 catalyst prepared via static hydrothermal method was characterized by X-ray diffraction(XRD), field emission scanning electron microscope(FESEM), X-ray photoelectron spectroscopy(XPS) and NH3-temperature programmed desorption(NH3-TPD). Under optimized conditions(using 1,4-dioxane as the solvent, 80 °C, 5 h, and air as the oxidant), the catalyst demonstrates excellent catalytic performance in the air-catalyzed epoxidation of 3-methyl-1-cyclohexene, achieving a substrate conversion rate of up to 97.2% and epoxide product selectivity ≥99%. Additionally, the catalyst demonstrates good substrate universality, achieving conversion rates of 79.4% and 80.3% for cyclooctene and 4-vinyl-1- cyclohexene, respectively, with corresponding epoxide product selectivities of 98.0% and 74.3%. After five cycles of use, the catalyst maintains stable catalytic activity, indicating excellent cyclic stability.
The electrocatalytic oxidation of propylene to 1,2-propylene glycol(PG) holds promise as a sustainable green chemistry approach. However, conventional palladium(Pd)-based catalysts are susceptible to CO poisoning and exhibit limited activity, which impedes their widespread application. To address the aforementioned challenges, an alloying strategy was employed in this study to design and synthesize a bimetallic oxide PdPbO x catalyst. A series of PdPbO x catalysts with varied Pd/Pb ratios were prepared through a chemical co-reduction method followed by high-temperature annealing. These catalysts were then evaluated for the electrocatalytic propylene oxidation reaction. Electrochemical measurements results reveal that the Pd0.256Pb0.045O x catalyst demonstrates superior electrocatalytic activity, achieving a PG production rate of 90.78 mmol·m-2·h-1 at 2.6 V(vs. RHE). The significant performance enhancement compared to the PdO catalyst is attributed to the multi-element synergistic effect exhibited by the bimetallic system. This effect effectively modulates the active site distribution and optimizes the electronic structure of the catalyst, providing new insights and directions for the design of highly efficient electrocatalytic propylene oxidation catalysts.
Quasi-spherical carbon nano-onions(CNOs) with a size of ca.5 nm were synthesized via thermal annealing of nanodiamonds. Subsequent oxidation using concentrated H2SO4/HNO3 introduced —COOH groups, yielding carboxylated CNOs(C-CNOs). Further functionalization through acylation and nucleophilic substitution produced highly phosphorylated CNOs(P-CNOs). High-resolution transmission electron microscopy(HRTEM), X-ray diffraction(XRD) and X-ray photoelectron spectroscopy(XPS) confirmed the successful introduction of —COOH and —PO3H2 groups, with P-CNOs exhibiting an ion exchange capacity(IEC) of 1.85 mmol/g. Homogeneous, intact, and dense SPAES/P-CNOs composite membranes were prepared via solution casting by blending P-CNOs with sulfonated poly(arylene ether sulfone)(SPAES). Compared to pristine SPAES, the composite membranes show enhanced properties including water uptake/swelling, oxidative stability, and proton conductivity. This improvement stems from hydrogen-bonding networks between the —COOH/—PO3H2 groups in P-CNOs and the —SO3H groups in SPAES, forming a more stable network structure that bolsters mechanical properties and chemical stability while facilitating proton transfer. The SPAES/P-CNOs-1.5 membrane achieves a high proton conductivity of 220 mS/cm at 90 °C. At 80 °C and 100% relative humidity(RH), its maximum power density reaches 650 mW/cm2, 36% higher than that of SPAES. It also shows excellent mechanical property and high thermal-dimensional-chemical stability, indicating significant application potential.
Biodegradable poly(lactic acid)(PLA) nanofibrous membranes(NFMs) can alleviate plastic pollution, aid in air quality improvement, and have gained significant attention in particulate matter(PM) filtration. However, they inherently lack gas selectivity; moreover, insufficient electroactivity and rapid charge dissipation lead to unstable PM filtration efficiency, which seriously restricts their development prospects. Herein, we employed a microwave-assisted method to fabricate high-selectivity active nanocrystals(HSANs), which were then integrated into PLA NFMs using a combined electrospinning⁃electrospray strategy, resulting in high-selectivity active(HSA) NFMs with a hierarchical porous structure. With the uniform, affinitive anchoring of HSANs(2%, 4% and 8%, mass fraction), the HSA NFMs thus obtained showed a significant increase in surface potential(up to 7.6 kV) and dielectric constant(1.68). Meanwhile, endowed with pronounced activity and optimized morphology, HSA NFMs exhibited PM2.5 and PM0.3 filtration efficiencies of 99.8% and 99.5% at 85 L/min, markedly outperforming Pure PLA(only 83.5% and 82.7%, respectively). Moreover, the prepared HSA NFMs exhibited excellent CO2 adsorption performance. Specifically, HSA-8 achieved the highest capacity of 57.2 cm3/g at 273.15 K/1.0 bar(1 bar=100 kPa), and its CO2/N2 selectivity of 40 was confirmed via ideal adsorbed solution theory(IAST) simulation. The proposed methodology exhibits an outstanding integration of high-efficiency CO2 capture and superior air filtration, which may facilitate the development of eco-friendly and functional protective membranes.
The "101 Plan" for basic disciplines is a foundational project initiated by the Ministry of Education to foster top-notch innovative talents. It aims to transform the talent training model from "knowledge-centered" to "competence-oriented" through reforms in basic elements such as curricula, textbooks, teaching staff, and practical projects. As a core foundational course in chemistry, Inorganic Chemistry directly impacts the training foundation of chemistry majors. Based on the construction requirements of the "101 Plan" of Chemistry, this paper systematically elaborates on the background of curriculum construction for Inorganic Chemistry, details the reconstruction ideas and specific content of the curriculum knowledge framework, and deeply analyzes the construction characteristics and application effects of dynamic electronic teaching materials and paper-based textbooks. This paper provides a reference for the reform of basic discipline courses.
Herein we comment on the application of theoretical computational data in organic chemistry education, using regioselectivity quantitative analysis and dynamic visualization of reaction mechanisms as examples. By calculating the structures and relative energy of possible transition states in epoxide ring-opening reactions, we successfully explained the regioselectivity of the reaction. Based on the quantitative analysis of the HOMO orbital coefficients of the reactant molecules, we revealed the differences in regioselectivity between naphth-1-ol and naphth-2-ol in electrophilic substitution reactions. Additionally, by utilizing precise theoretical computational data, we created animations showing structural changes and variations in orbital shapes during both Finkelstein reaction and elimination reaction processes, achieving dynamic visualization of the SN2 and E2 mechanisms for teaching purposes. These practices demonstrate that the application of theoretical computational data has infused new vitality into organic chemistry education, not only helping students understand abstract chemical concepts more intuitively but also providing significant support for the innovation of teaching methods, with notable educational value and potential for widespread adoption.