Amentoflavone (Ame) is a kind of precious biflavonoid with various bioactivities. To further develop and use Ame, Ame was extracted and purified from Ginkgo biloba leaves, and Ame complexes with metal ions (Mn2+/Fe3+/Co2+/Ni2+/Cu2+/Zn2+) were synthesized for the first time. The structures of Ame complexes were characterized using UV/vis, FT-IR, HRMS and DFT calculations. Their antioxidant activity was evaluated using pyrogallol auto-oxidation and ABTS methods. DNA binding affinity was explored via fluorescence studies and molecular docking simulations. The structural analysis indicated that the stoichiometric ratios of Ame and Mn2+/Co2+/Ni2+/Cu2+/Zn2+ were 1 : 1, and the chelation sites were between the 5 ''-hydroxyl and 4 ''-carbonyl, while the stoichiometric ratio of Ame and Fe3+ was 2 : 2, and the chelation sites were between the 5 ''-hydroxyl and 4 ''-carbonyl and the 5-hydroxyl and 4-carbonyl. The investigation of pyrogallol auto-oxidation and ABTS methods demonstrated that Ame complexes had superior scavenging activities for O2-(center dot) and ABTS+(center dot) free radicals. What's more, free radical scavenging activity of some Ame complexes was stronger or similar compared with VC. The results of fluorescence studies indicated that Ame complexes had a stronger DNA binding affinity with intercalation mode. A molecular docking study confirmed that Ame and its complexes interacted with DNA via van der Waals forces, conventional hydrogen bonding and pi-pi stacking effects. These results demonstrated that bioactivities of Ame could be enhanced via forming complexes with metal ions and provided theoretical support for the application of biflavonoids as potential drugs, dietary supplements and cosmetic agents.

To address the high systemic toxicity associated with cisplatin-based anticancer drugs, copper (II) complexes have emerged as promising alternatives due to the essential and endogenous role of copper in human physiology. In this study, three novel Cu (II) complexes - [CuL (OAc)] center dot 2H2O) (C1), [CuL (NO3)(H2O)] (C2), and [Cu2L2Cl2] (C3) - were designed and synthesized using a coumarin-3-formyl-(2-aminomethylpyridine) ligand (L). Structural characterization revealed that C1 and C2 are mononuclear copper (II) complexes with a pentacoordinate distorted square pyramidal geometries, while C3 features a unique binuclear copper (II) structure. In vitro anticancer assays demonstrated that all three compounds exhibited significant cytotoxicity against HeLa cervical cancer cells. with C1 showing particularly remarkable activity (IC50 = 0.8964 +/- 0.09 mu M). Moreover, C1 displayed lower toxicity to normal cells, and its selectivity index (SI) was 522 times greater than that of cisplatin. Mechanistic studies revealed that C1 induces dose-dependent apoptosis in HeLa cells and arrests the cell cycle at S phases. Spectroscopic analyses (UV-Vis, fluorescence, viscosity) and molecular docking confirmed that these complexes bind to DNA through intercalation mediated by non-covalent interactions such as hydrogen bonding and pi-pi stacking, elucidating the structural basis for their anticancer activity. These findings highlight the potential of C1 as a highly selective and effective candidate for targeted cancer therapy, warranting further development and evaluation.

The catalytic asymmetric Michael addition of α,β-unsaturated carbonyl compounds is one of the most valuable methods for constructing the β-carbon chirality centre because of its atom economy and efficiency. However, the catalytic asymmetric reverse α-addition of a nucleophile to an α,β-unsaturated carbonyl compound is much less common. Here we realize a palladium-catalysed asymmetric α-carboranylation of α,β-unsaturated carboxylic acids via an inverse electron-demand nucleophilic addition. The reaction features good B(9)-site selectivity of o/m-carboranes, precise α-regioselectivity towards α,β-unsaturated carboxylic acids, wide functional group tolerance and excellent enantioselectivities. A detailed reaction mechanism is proposed based on experimental and computational results that elucidates the origin of the enantioselectivity and α-selectivity. This finding has a guiding significance for the catalytic asymmetric anti-Michael-type addition of α,β-unsaturated carbonyl compounds and provides a different avenue for synthesizing α-chiral carboxylic acids. The catalytic asymmetric Michael addition to α,β-unsaturated carbonyl compounds is one of the most valuable methods for the construction of β-carbon chiral centres. Now the authors report a Pd-catalysed asymmetric anti-Michael-type addition of carboranes to α,β-unsaturated carbonyl compounds.

A binuclear Cu(ii) complex, [Cu2L2(OAc)4]< middle dot > H2O (Coupy-Cu), with 3-(pyridin-3-yl) coumarin as the ligand, was synthesized by the slow solvent evaporation method. Complex Coupy-Cu was characterized by elemental analysis and infrared spectroscopy, and its crystal structure was determined by X-ray single-crystal diffraction, revealing a distorted octahedral geometry around each copper center. The antiferromagnetically coupled dimeric structure was further confirmed by EPR and VSM, which indicated a diamagnetic singlet ground state (S = 0) with weak paramagnetic susceptibility. Complex Coupy-Cu exhibited favorable cytotoxic activity against a panel of human cancer cell lines (HeLa, A549, MCF-7, and HepG2), with anti-proliferative efficacy against HepG2 cells superior to that of oxaliplatin and induced 43.3% apoptosis at 20 mu M in a concentration-dependent manner. It is worth emphasizing that the complex showed significantly lower toxicity toward normal cells compared to cisplatin and oxaliplatin, displaying a safety index 5.2 times that of oxaliplatin and 30.4 times that of cisplatin. Investigations via electronic absorption spectroscopy, fluorescence spectroscopy, viscosity measurements, and molecular docking indicated that the complex binds to calf thymus DNA (CT-DNA) primarily through an intercalative mode. This binding was further validated via molecular dynamics simulations, which demonstrated stable complex formation and a calculated binding free energy of -13.74 kcal mol-1, driven predominantly by van der Waals interactions.

ABSTRACT With the deepening mechanistic understanding of intermolecular spatial interactions, dimers, the simplest and most fundamental aggregated architecture, emerge as a versatile platform for the rational design and development of high‐performance aggregated luminescent materials. Herein, we report that a specific class of coumarin derivatives with dihydrazide units spontaneously forms the biomass‐based dimers in both aggregated and solid states, exhibiting pronounced red‐shifted emissions. Mechanistic investigations further reveal that these well‐defined dimeric assemblies come from molecular planarization induced by dihydrazide and salicyl units, heteroatom‐involved spatial interactions, and steric hindrance imposed by chlorine atoms, which synergistically orchestrate the aggregation‐induced red‐shifted emission. Notably, these coumarin‐derived dimers exhibit an intriguing force‐activated thermal responsiveness. Mechanical force modulates the packing modes of dimeric assemblies, enabling reversible thermochromic fluorescence. As a practical demonstration, coumarin derivatives integrating both thermochromism and acidichromism are successfully employed for dynamic information decryption, highlighting their potential in intelligent anti‐counterfeiting. This work successfully constructs high‐performance aggregated luminescent materials based on biomass‑based dimers and exploits their unique force‑activated thermochromic responsiveness to extend applications in intelligent anti‑counterfeiting.

A benzothiazole-modified quinoline Schiff base fluorescence probe TQ was designed synthesized to detect Zn 2+ in living cells and real water samples.

In pursuit of more effective anticancer treatments, we developed a series of innovative dehydroabietylamine (DHAA) derivatives, with particular emphasis on introducing nitro modifications to the C-ring based on incorporating C-18 Schiff base heterocyclic structures. We evaluated the cytotoxic effects of these compounds in vitro against a panel of human tumor cell lines - MCF-7 (breast cancer), A549 (lung cancer), HeLa (cervical cancer), and HepG2 (liver cancer) - as well as the non-malignant cell line HUVEC (human umbilical vein endothelial cells). DHAA derivatives L15 and L20, with C-ring 14-nitro substitution based on C-18 Schiff base heterocyclic modification, showed higher cytotoxic activity against HeLa and A549 cells, respectively, while demonstrating significantly lower cytotoxicity to non-malignant HUVEC cells. Meantime the mechanism of cytotoxicity of DHAA derivatives was preliminarily investigated. The result suggested that inducing cell apoptosis might be the primary mechanism. The interaction between DHAA derivatives and HS-DNA was studied using absorption spectral analysis and ethidium bromide (EB) fluorescence displacement experiments, the results exhibited that the binding of DHAA derivatives to DNA was in the intercalative mode. The molecular docking study demonstrated that DHAA derivatives exhibited a strong binding affinity to DNA, facilitated by carbon‑hydrogen interactions and π-donor hydrogen bonds. The structure-activity relationship discussion implied that introduction of the nitro-group, especially the 14-nitro group, significantly improved the cytotoxicity of DHAA. The significant cytotoxicity and high selectivity exhibited by compounds L15 and L20 suggested their potential as promising antitumor medicines.

A series of Dehydroabietylamine (DHAA) C-ring Schiff derivatives, L3-L20, were synthesized and their in vitro cytotoxic activity against the human tumor cell lines cervix HeLa, breast MCF-7, lung A549, liver HepG2, and the nonmalignant cell line umbilical vein HUVEC was investigated. Most of the compounds showed varying degrees of anticancer activity against HeLa cell lines while demonstrating lower toxicity to normal HUVEC cells compared to DHAA and doxorubicin (DOX), especially compound L19, which not only enhanced the anticancer activity of DHAA, but also significantly reduced the toxicity to normal cells, achieving a selectivity index (SI) 118 times higher than that of DHAA and 245 times higher than that of DOX. In addition, Compound L19 induced apoptosis in HeLa cells in a dose-dependent manner, suppressed the expression of the anti-apoptotic protein Bcl-2, and arrested the cell cycle at the S phase. Spectroscopic experiments and molecular docking results showed that there was a strong interaction between the compounds and DNA. All these results indicate that the introduction of Schiff base structure on the C-ring of DHAA is an effective strategy for enhancing its selectivity, providing new insights for the design of DHAA-based anticancer compounds.

A photoelectrochemical (PEC) sensor based on the poly-2,2,5,2-terthiophene (pTTh)/Cu2O heterojunction was constructed and applied for the detection of long non-coding RNA (lncRNA) TROJAN, a biomarker of triple-negative breast cancer. Cu2O and pTTh were electrodeposited in situ and sequentially onto an indium tin oxide substrate. The bandgap of the resultant type II heterojunction was measured spectroscopically and the morphology was found to effectively separate photogenerated holes from electrons. A photocurrent density as high as 250 μA cm-2 was attained, which is about three times higher than those of only pTTh or Cu2O. Owing to the close contact between pTTh and Cu2O, this PEC sensor is highly stable. Oligonucleotide probes for lncRNA can be cross-linked to carboxyl moieties of mercaptopropionic acid molecules adsorbed on pTTh/Cu2O. The desirable band structure and the high density of probe molecules collectively yielded a linear range of 0.1-10 000 pM. Our PEC sensor has been demonstrated to be amenable for detection of lncRNA markers with excellent analytical performance.

Endowing thermally activated delayed fluorescence (TADF) emitters simultaneously with high emission quantum yields and short radiative lifetimes is of fundamental significance in optoelectronic field. In this contribution, two neutral tetrahedral Cu(I) complexes (1 and 2) have been developed, which realize blue-TADF with photo-luminescent quantum yield of up to 85 % due to the high structural rigidity. Meanwhile, short TADF lifetimes (<10 mu s) of the Cu(I) complexes suggest that the synergistic effects of small Delta E(S1-T1) gap and relatively large SOC value introduced by the copper ion could facilitate fast reverse ISC processes compared to the typical organic-TADF materials.

Zinc is an essential trace element and its deficiency has been related to skin conditions, Alzheimer’s disease, and some types of cancer. Therefore, detecting zinc ions in the human body with high sensitivity is important. Here, two “turn-on” quinoline-based fluorescent probes (E)-2-((2-(quinolin-2-yl) hydrazono) methyl) phenol (QSP-H) and (E)-4-chloro-2-((2-(quinolin-2-yl) hydrazono) methyl) phenol (QSP-Cl) were fabricated for the detection of Zn2+. Both the QSP-H and QSP-Cl revealed low LOD (71 nM for QSP-H, 67 nM for QSP-Cl) and high selectivity, and worked across a broad pH range (3 ‒12 for QSP-H, 3 ‒11 for QSP-Cl). The HRMS, 1H NMR titration, DFT calculations and Job’s plot analysis were employed to explore the mechanism of Zn2+ detection through QSP-H and QSP-Cl. QSP-H and QSP-Cl were effectively applied to the quantitative assessment of Zn2+ in two infant formula samples and to the bioimaging-based detection of exogenous Zn2+ in living cells.

While the existing university chemistry experimental teaching content is comprehensive,it often lacks a connection with cutting-edge scientific research,particularly in trending fields.In this study,we introduce the experiment"Kaempferol as an AIE-active natural product probe for selective Al3+detection"into teaching practice.Through this experiment,students gain an understanding of the contributions made by Chinese scientists in the field of aggregation-induced emission(AIE)research.They also learn about the fundamental principles and applications of fluorescence,and gain intuitive insights into the distinctions between aggregation-induced emission and aggregation-induced quenching.The experiment encompasses complex structure analysis,spectral analysis,and instrumental characterization,offering both comprehensiveness and ease of operation.By engaging in this teaching practice,students develop their innovative thinking and comprehensive abilities,while simultaneously reinforcing their commitment to environmentally friendly development and enhancing a sense of national pride.

In this work, we developed a facile and controllable electrophilic aromatic nitration method with commercially available 68% HNO3 as the nitrating reagent and trifluoromethanesulfonic acid (HOTf) as the catalyst in hexafluoroisopropanol or under solvent-free conditions. The electrophilic nitration products of different arenes can be obtained in almost quantitative yields by tuning the loading of HOTf. The strong acidity and water absorbing property of HOTf allowed this transformation to reach completion in a short time at room temperature.

Four neutral mononuclear copper(I) complexes (1-4) with formula of [(N boolean AND P)Cu(PPh3)(2)] (1-2) and [(N boolean AND P)Cu (Xantphos)] (3-4) based on NH-deprotonated (2-(1H-benzimidazole)phenyl) diphenylphosphine ligands (N boolean AND P) and phosphine ancillary ligands have been synthesized. The copper(I) complexes exhibit bright thermally acti-vated delayed fluorescence at room temperature with photoluminescence quantum yield up to 43.5%. Upon grinding, the complexes display apparent bathochromic shift in the emission maxima of up to 50 nm (1). Meanwhile, the complexes display similar luminescence profiles to those of the origin samples exposed to CH3OH vapor. Single crystal X-ray and PXRD diffraction results demonstrate that the reversible mechanochromic luminescent (MCL) properties are ascribed to the transformation of crystalline and amorphous state dependent on the disruption and restoration of hydrogen bonds during external stimuli, which have been rarely observed in the copper(I)-based MCL materials hitherto. These findings clearly suggest that the introduction of switchable secondary interactions in mononuclear copper(I) complex is a large-scale synthesis strategy for multifunctional luminescent materials.

The azobenzene coumarin derivatives 2-10, in which the coumarin moiety is linked to substituted phenyl and pyridine groups via amide bonds, and a copper complex with compound 8 (8-CuCl2) were designed and synthesized, and their anticancer activities were investigated. Compounds 2-10 and 8-CuCl2 exhibited different degrees of anticancer activities against four cancer cell lines (HeLa, A549, MCF-7, and HepG-2). Among them, compound 6 exhibited stronger cytotoxicity (IC50 = 0.51 +/- 0.22 mu M) against A549 cell lines and was less toxic to normal cells than Doxorubicin (DOX) (IC50 = 1.18 +/- 0.03 mu M). Compound 8 exhibited stronger cytotoxicity against MCF-7 cell lines than DOX with an IC50 value 48 times higher than DOX (IC50 = 0.42 +/- 0.23 mu M for 8; IC50 = 20.64 +/- 3.67 mu M for DOX). Meanwhile, compound 8 was much less toxic to normal human umbilical vein endothelial cells (HUVEC) cells than DOX with a 3000 times higher selectivity index (SI) (SI > 238.10 for 8; SI = 0.078 for DOX). The results of cell apoptosis and cycle assays showed that compound 6 induced apoptosis in A549 cells more considerably and blocked cells in the S phase, whereas compound 8 induced late apoptosis in MCF-7 cells and blocked cells in the S phase. Ultraviolet and fluorescence spectroscopy analyses revealed that compounds 6 and 8 bound to deoxyribonucleic acid (DNA) via intercalation. In summary, compound 8 was developed as a potential and effective cytotoxicity against MCF-7 cell lines worthy of further investigation.

This work describes the synthesis, anticancer activity and electron structure study of two Cu (II) complexes with coumarin-3-formyl-(3-(aminomethyl) pyridine) ligand (L) - C1 (Cu2L2(OAc)4) and C2 (CuL2(NO3)2). The structure of C1 and C2 was confirmed by elemental analysis, FTIR, and single-crystal X-ray analysis. Complex C1 crystallizes as binuclear where two Cu (II) ions are bridged by four acetate ligands while C2 is a mononuclear complex with twisted octahedral geometry. Density functional theory (DFT) calculations revealed that electronic transitions originate from metal-ligand charge transfer and d-d transitions of metal ions. According to the results of UV-Vis and fluorescence titrations, C1 and C2 intercalate with DNA with the binding constants of 6.9 × 105 M-1 and 5.9 × 105 M-1, respectively. The in vitro cytotoxicity assays on four cancer cell lines (HeLa, HepG2, MCF-7 and A549) and a normal HUVEC cell line indicated higher anti-MCF-7 activity of C2 compared with cisplatin (IC50 = 2.86 ± 0.08 μM vs. 9.07 ± 0.10 μM). Moreover, C2 had superior selectivity since IC50 toward HUVEC cells was over 150 μM compared with 0.58 ± 0.05 μM for cisplatin. We concluded that the anti-MCF activity of mononuclear C2 complex is better than that of binuclear C1 and cisplatin. Therefore, C2 has been selected as a hit compound to develop novel non‑platinum anticancer agents through modification of coumarin-amide structure and variation of copper (II) salts.

A facile halogenation method for highly selective synthesis of 9-X-o-carboranes, 9,12-X2-o-carboranes, 9-X-12-X'-o-carboranes, 9-X-m-carboranes, 9,10-X2-m-carboranes, and 9-X-10-X'-m-carboranes (X, X' = Cl, Br, I) has been developed on the basis of our previous work. The success of this transformation relies on the usage of trifluoromethanesulfonic acid (HOTf), the easily available strong Brønsted acid. The addition of HOTf greatly increases the electrophilicity of N-haloamides through hydrogen bonding interaction, resulting in the low loading of N-haloamides, short reaction time, and mild reaction conditions. Additionally, the solvent 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) is also essential to further increase the acidity of HOTf.

香豆素是一种重要的天然产物,同时具有优良的生物活性和光学活性.阴离子广泛存在于生命体和自然环境中,对人类的生活有着巨大的影响,因此开发能够特异性检测某种阴离子的荧光探针具有非常重要的科学意义.主要总结了近几年香豆素类阴离子荧光探针的研究进展,重点讨论了检测F-、ClO-、ONOO-以及一些其他阴离子的香豆素类荧光探针的设计合成、响应机制及在环境及生物体中的应用.为进一步设计与构筑新型阴离子荧光探针奠定基础.