Four coumarin-based molecular probes were synthesized via the reaction of phenylhydrazine and coumarin derivatives. Their binding properties toward various anions (F-, Cl-, Br-, I-, SO32-, H2PO4-, CH3COO-, HS-) and cations (Li+, Na+, Mg2+, Al3+, K+, Mn2+, Fe3+, Co2+, Ni2+, Cu2+, Cd2+) were systematically investigated using UV-Vis absorption spectroscopy, fluorescence spectroscopy and cyclic voltammetry. The results demonstrated that the probes exhibited high selectivity, sensitivity and specificity for Cu2+, Co2+, Fe3+ with distinct colorimetric changes upon host-guest interaction, enabling visual detection. These findings establish a promising approach for trace ion sensing. Theoretical studies revealed that the observed red shifts in the UV-Vis spectra originated from electron transitions involving the highest occupied molecular orbital (HOMO). Furthermore, cytotoxicity assays confirmed the probes' biocompatibility, suggesting their potential for intracellular ion detection in living cells.

The experimental results showed that the limiting oxygen index (LOI) value of the THPON3-THPC-treated cotton fabric increased significantly (by up to 32.5%), and the length of damage in the vertical burning test was reduced to 8.1 cm with no afterflame. Cone calorimeter tests revealed a significant reduction in combustion efficiency, with the peak heat release rate (PHRR) decreasing from 283.1 to 112.9 kW/m2 and the total heat release (THR) decreasing from 21.8 to 4.6 MJ/m2. Compared to the traditional Proban ammonia curing process, THPON3-THPC demonstrated greater flame-retardant effectiveness. This treatment improved both the comfort and environmental sustainability of the flame-retardant cotton fabric. Furthermore, experimental results showed that THPON3 achieved formaldehyde removal rates of 92.5% (E2 grade) and 68.3% (NAF grade) from plywood, outperforming urea and demonstrating significant formaldehyde removal capabilities. As an efficient formaldehyde scavenger, THPON3 significantly inhibited and delayed the release of formaldehyde from plywood. Additionally, cytotoxicity tests showed that THPON3 exhibited no significant toxicity to Hacat and BEAS-2B cells at a concentration of 800 mu M, indicating a very low risk to human health in the event of accidental ingestion or inhalation. These findings are important for the application of THPON3 in flame-retardant and residential building materials.

Herein for the first time, we disclose a practical and straightforward approach to access α-SF5 ketones via direct oxypentafluorosulfanylation of alkynes with SF5Cl and oxygen under acidic conditions by one step. The protocol features mild reaction conditions, broad substrate scope, good functional group compatibility and can be applied to late-state functionalization of complex natural products and pharmaceuticals. A radical mechanism involving SF5 radical addition to triple bonds followed by O2 capture is proposed.

The electrophilic trifluoromethylselenolation cyclizations of propargylic amides are disclosed. The transformations undergo the 6-endo-dig and 5-exo-dig cyclizations to synthesize SeCF3-substituted oxazines and oxazolines, respectively, which are induced by N-trifluoromethylselenophthalimide. This protocol is suitable for late-stage applications of complex natural products and drug molecules.

An expedient strategy for the construction of trifluoromethylselenolated spiro[5.5]trienones/spiro[4.5]trienones through a cascade electrophilic trifluoromethylselenolation cyclization and dearomatization has been developed. This sequential process was induced by N-trifluoromethylselenophthalimide (Phth-SeCF3), which was an efficient electrophilic trifluoromethylselenolation reagent. This approach has the feature of mild conditions, broad substrate scope, and high functional group tolerance.

It is key to develop novel economical and effective non-noble metal bifunctional catalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting cells. Herein, a series of novel twodimensional (2D) ultrathin donor-acceptor Co-based metal organic framework nanoplates (U-DA-CoMOF-NPs) as bifunctional HER/OER catalysts have been designed and fabricated based on a donor-acceptor strategy. Density functional theory calculations demonstrate that the fabricated U-DA-CoMOF-NPs are fine donor-acceptor pairs having HOMO-LUMO localizations and a HOMO-LUMO gap of 2.60 eV and give the Gibbs free energy for a reasonable OER mechanism. Additionally, changes in anions can affect the physicochemical characterizations and HER/OER performance of the fabricated U-DA-CoMOF-NPs. As a result, the fabricated U-DA-CoMOF-NPs-1 using NO3- as an anion exhibits the optimal HER/OER performance in alkaline solution thanks to the thinnest nanoplate thickness, the largest surface area and hierarchical mesoporous structure. Moreover, a self-assembled overall water splitting cell with U-DA-CoMOF-NPs-1/NF as both cathode and anode achieves a low potential of 1.65 V and a high cycling stability at 10 mA cm-2 for at least 15 h. The present study offers an option to design and fabricate other cost-effective donor-acceptor MOF-based catalysts for water splitting cells.

Porous organic polymers (POPs) are promising candidates for catalyzing the hydrogen evolution reaction (HER) and the oxygen reduction reaction (ORR) owing to their tunable porous structures and abundant chemical reaction channels/active centers. However, insufficient conductivities limit their practical applications in the HER/ORR. The challenge is to construct conductive POPs with highly efficient HER/ORR performance. Herein, a series of metal-free corrole-based donor-acceptor POPs (Cor-D-A-POPs) as bifunctional HER/ORR catalysts have been designed and constructed from 5,10,15-tris(p-aminophenyl)corrole (TPAPC) and 2,2 '-bithiophene-5,5 '-dialdehyde (BTDA) or 2,5-thiophenedialdehyde (TDA) with a donor-acceptor method. Compared with Cor-D-A-POPs using TDA as an electron donor (Cor-TDA-D-A-POPs), Cor-D-A-POPs using BTDA as an electron donor (Cor-BTDA-D-A-POPs) exhibit higher HER/ORR activities due to their more favorable charge transfer ability from the BTDA donor to the TPAPC acceptor. The integration of high surface area, rich accessible catalytic sites, and high conductivity makes Cor-BTDA-D-A-POP-1 constructed in a mixed solvent of n-butanol/mesitylene (1 : 1) exhibit optimal HER/ORR activities in alkaline solution, with a comparable HER overpotential of 0.10 V at 10 mA cm-2 and an ORR Tafel slope of 90.0 mV dec-1 to Pt/C (0.09 V and 88.0 mV dec-1). Moreover, its HER/ORR stability is superior to that of Pt/C. The experimental results are consistent with density functional theory calculations. Therefore, the combination of suitable electron donors and electron acceptors can promote charge transfer within POPs and generate high activities for the HER/ORR. Metal-free corrole-based donor-acceptor porous organic polymers (Cor-D-A-POPs) are constructed and are active for the HER/ORR. By tuning the electron donor and mixed solvent, Cor-BTDA-D-A-POP-1 shows the best activity among all constructed catalysts.

The exploration of economical and effective non-noble metal catalysts is essential for oxygen reduction reaction (ORR) in energy devices. Recently, heteroatom-doped metal-organic frameworks (MOFs) have shown great potential in ORR due to their high efficiencies and low costs. Herein, three-dimensional (3D) urchin-like N/S co-doped Mn-based MOFs (U–N/S–Mn-MOFs) as an effective ORR catalyst have been successfully prepared by a facile one-step solvothermal methodology. The unique 3D urchin-like structure with a spherical interior and dendritic exterior may provide more catalytic sites and transport channels for ORR. Simultaneously, the doped N and S combined with Mn can promote oxygen adsorption and reduce the reaction energy barrier. These characteristics endow U–N/S–Mn-MOFs with high ORR performance. The present work provides a new opportunity for multiple heteroatom-doped MOFs to achieve high electrocatalytic performance.

Abnormal copper ions (Cu2+) and biothiols have potential impacts on environmental pollution and human health, so the detection of these substances with high selectivity and sensitivity has become an important research topic. In this study, we designed and synthesized two fluorescent probes (L1 and L2) based on naphthalene and anthracene derivatives that could specifically detect Cu2+ and biothiols. Owing to the paramagnetic effect of Cu2+, the strong fluorescent intensity was quenched after the addition of Cu2+. When biothiols were added to the solution (L-Cu2+), the fluorescence intensity was significantly enhanced and recovered. So, the interaction process was accompanied with "ON-OFF-ON" phenomenon in fluorescent intensity. Two complexes (L-Cu2+) showed low limit of detection for biothiols (Cys was 3.4 ×10-5 M and GSH was 2.0 ×10-5 M) and weak cytotoxicity (< 150 μg/mL). Theoretical investigation analysis revealed that the intramolecular hydrogen bond existed in the structure of probes and the roles of molecular frontier orbitals in molecular interplay. In addition, two probes also showed good applicability in actual drug Atomolan. The GSH content in the tested Atomolan reached over 99.9% of the labeling which was accord with the percentage of pharmacopoeia. Therefore, two probes have the real application value in the detection of Cu2+, biothiols and drug efficacy in various environments.

A new electrophilic trifluoromethylselenolation reagent, N-trifluoromethylselenophthalimide (Phth-SeCF3), was developed. A strategy for the synthesis of 4-trifluoromethylselenolated isoxazoles through electrophilic trifluoromethylselenolation cyclization has been established by using Phth-SeCF3 as an electrophilic reagent. Moreover, this protocol has the features of broad substrate scope, good functional group tolerance, and high yields.

In order to better monitor the content of Fe 3+ and H 2 S in the biological environment, two new fluorescent probes were designed and synthesized. With the addition of Fe 3+ , the strong fluorescence emission of two probes was significantly quenched due to the paramagnetic effect of Fe 3+ . With the further addition of S 2− , the fluorescence intensity was quickly restored. Two probes showed high selectivity and strong sensitivity for the detection of Fe 3+ and S 2− , and the fluorescence intensity “ON-OFF-ON” was accompanied with the interaction process. At the same time, two probes displayed good anti-interference ability which was not interfered by the existence of other ions. In addition, two probes illustrated fast response time to Fe 3+ , S 2− and small cytotoxicity to cells. Therefore, two probes can provide a potential ideal tool for detecting Fe 3+ and H 2 S in organisms and the environment.

A novel free-halogen flame retardant (trimethylolphosphine carbamate, THPON) was synthesized through the simple reaction between tetrakis(hydroxymethyl) phosphonium chloride and urea. Small molecule THPON could infiltrated the cotton fibers and grafted on cotton cellulose by amide bond. What is more, THPON did not change the inherent crystal structure of cotton because it infiltrated into the amorphous region of cotton. THPON-treated cotton was easily decomposed into phosphoric acid or polyphosphate at lower temperature and exhibited good flame retardancy due to the N/P synergistic effect. Compared to control, the heat release rate of THPON-treated cotton increased slower, indicating that a protective carbon layer formed and acted as a barrier. In addition, THPON displayed the low cytotoxicity and biosafety. The development and properties of THPON could provide an important data for the further application in the industry.

Two colorimetric and fluorescent probes based on ferrocene derivatives have been designed and synthesized. Among studied anions (F-, AcO-, H2PO4-, Cl-, Br- and I-), probe 1 with p-nitrophenyl hydrazine structure has the strongest binding ability for F-, as well as probe 2 for H2PO4-. It had strong binding ability and was not affected by other anions. The determination limit of 1 toward F- was 5.0x10(-6) mol.L-1 which can be used for the trace detection of F-. The interacted process of host-guest accompanied by colorimetric changes and increment in fluorescent intensity of the probes. A H-1-NMR titration experiment and theoretical investigation indicated that -NH in hydrazine participated in the interaction, and the hydrogen-bonding formed between the probes and anions. These results provided an essential clue to the developing the colorimetric probe based on hydrazine participation.

Design and development of cost-efficient multifunctional three-dimensional (3D) metal organic frameworks (MOFs) towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are very significant for green energy devices. Herein, a scalable one-pot solvothermal method is developed to obtain a series of multifunctional 3D flower-like MOFs. In addition, systematic studies are also conducted on the effects of various metal cations and N-containing ligands on the structures, compositions, and multifunctional performance of the obtained MOFs. As a result, 3D flower-like Co-MOFs using Co2+ as a metal cation and 2,2’:6′,2″-terpyridine as a N-containing ligand exhibit the highest multifunctional performance towards ORR, OER and HER. The scalable method provides a new prospect to design and develop other MOFs-based multifunctional catalysts.

以硝基取代苯肼和苯甲醛衍生物为原料,设计并合成了一系列含有苯肼类硫化氢荧光分子探针.通过紫外-可见光谱、荧光光谱等实验测定了探针与生物重要阴离子(HS-,H2 PO-4,AcO-,F-,Cl-,Br-,I-)及硫醇(Cys,GSH,Hcy)的相互作用,分析了主客体可能的作用机制,筛选出具有高选择性和高灵敏度的荧光探针.结果表明,荧光探针1+Cu2+对HS-的结合能力最强,且显示较高的选择性和灵敏度.此外,该探针对人肝癌细胞(HepG-2)的毒性较小,可为肝癌的早期诊断与预防提供重要依据.

A method to synthesize benzofurylselenocyanates, benzothienylselenocyanates and indolylselenocyanates via electrophilic selenocyanogen cyclization was established. This sequential process was conducted under mild conditions in a short time. This protocol was successfully applied to late-stage functionalization of bioactive molecules. Notablely, the selenocyanate can be converted into other valuable Se-containing compounds and showed antitumor activity to human hepatoma cells HepG2.

A strategy for the synthesis of isoquinolylselenocyanates and quinolylselenocyanates through electrophilic selenocyanogen cyclization has been developed. The feature of this reaction is that the sequential process was induced directly by generated in situ pseudohalogen (SeCN)(2) generated in situ. Additionally, the obtained selenocyanates allowed functional group diversification, which could be potential intermediates for valuable compounds.

形成性评价体系由线上评价和线下评价组成,线上评价依托超星学习通教学平台进行,线下评价以学生和教师为评价者,采用多种评价方式对学生的学习过程、学习态度及情感等方面进行评价,教师分析总结评价结果,及时制订适合学生学习的教学方案,学生根据教师的反馈结果及时解决学习中的问题,形成以评促学和以评促教的教学环境.教学实践表明,形成性评价体系有助于形成积极向上的教风和学风,活跃学习气氛,使教学质量得以明显提高.

A practical strategy for the synthesis of spiro[5.5]trienones-fused selenocyanates and spiro[4.5]trienones-fused selenocyanates through electrophilic selenocyanogen cyclization and dearomative spirocyclization is reported. This approach was conducted under mild conditions with broad substrate scope and good functional group tolerance. The utility of this procedure is exhibited in the late-stage functionalization of nature product and drug molecules.

课程思政是高校落实立德树人根本任务的新举措,是无机化学一流课程建设的核心和关键.本文立足无机化学课程特点和教学实际,探讨了药学专业无机化学实施课程思政的必要性,将其中蕴含的思政教育元素潜移默化地渗透到课堂实践中,竭力培养学生的探究精神和创新意识,塑造学生明辨性思维和环保理念,提升学生的文化自信和家国情怀,为建设一门"知识传授、能力培养、价值塑造"三位一体的一流课程提供改革思路和方法.