A Catalyst‐Free Aqueous Synthesis of 2‐Amino‐7,9‐dihydrothieno[3′,2′:5,6]pyrido[2,3‐d]pyrimidine‐4,6(3H,5H)‐dione Derivatives

A series of novel 7,9‐dihydrothieno[3′,2′:5,6]pyrido[2,3‐d]pyrimidine‐4,6(3H,5H)‐dione derivatives were synthesized efficiently via the catalyst‐free reaction of aldehyde, ethyl 2,4‐dioxotetrahydrothiophene‐3‐carboxylate, and 2,6‐diaminopyrimidine‐4(3H)‐one through the sequence of deethoxycarbonylation and three‐component condensation in aqueous media. This protocol featured mild reaction conditions, high yields, easy work‐up, and environmentally friendly procedure.     

The Crystal Structure and Synthesis Mechanism of 3,6‐Bis(3,5‐dimethylpyrazol‐1‐yl)‐1,4‐dihydro‐1,2,4,5‐tetrazine (BDT): A Key Precursor of S‐tetrazine

The single crystal structure of 1,1′‐bis (3,5‐dimethyl‐pyrazole) methenehydrazine (BDM) was determined by X‐ray single crystal diffraction for the first time. The obtained experimental results indicated that BDM was the intermediate of 3,6‐bis(3,5‐dimethylpyrazol‐1‐yl)‐1,4‐dihydro‐1,2,4,5‐tetrazine (BDT), which was the key precursor of s‐tetrazine. By this evidence, the preparation mechanism of BDT was proved: At 318.15 K, triaminoguanidine and pentanedione reacted to achieve the intermediate (BDM) by molecular nucleophilic addition and intramolecular nucleophilic substitution; when heated to 363.15 K, BDT was then generated by two molecules of BDM with nucleophilic substitution reaction. Furthermore, the thermal decomposition properties and also the non‐isothermal kinetic parameters have been investigated in the present work.     

Synthesis,Characterizations, Magnetism and Thermal Degradation of a 2‐Fold Interpenetrated 3D Cobalt‐Organic Framework

A new coordination polymer, [Co₂(L)₂(4,4′‐bipy)]_n·3nH₂O ( 1 ) based on 5‐(3‐methyl‐5‐phenyl‐4H‐1,2,4‐triazol‐4‐yl)isophthalic acid (H₂ L ) and 4,4′‐bipyridine (4,4′‐bipy) has been hydrothermally synthesized and characterized by single‐crystal X‐ray diffraction, XRPD, IR, and elemental analysis. Temperature‐dependent magnetic susceptibility and thermal degradation for 1 were also studied. The asymmetric unit of compound 1 consists of two crystallographically independent Co(II) ion, two L ^2? ligand, one 4,4′‐bipy ligand, and three lattice water molecules. The 2D triangle networks were linked by the bridging 4,4′‐bipy ligand to give rise to a 2‐fold interpenetrated 3D architecture. The simplest cyclic motif of the 2D networks is a triangle ring consisting of three Co(II) cations and three L ^2? ligands. So we can define Co(II) ions as 4‐connected nodes and the L ^2? ligands as 3‐connected nodes. Thus, the 3D structure can be described as a 2‐fold parallel interpenetrated ins InS 3,4‐conn topology.     

Preparation of Fluorescent Polystyrene via ATRP with Dimethylamino Chalcones as Initiator

4‐(3‐(4‐(Dimethylamino)phenyl)acryloyl)phenyl‐2‐bromo‐2‐methylpropanoate (APPBr) was used for the heterogeneous atom transfer radical polymerization (ATRP) of styrene (St) with copper(I) bromide/N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine (PMDETA) catalytic system. The functional end group was characterized via UV‐Vis and ¹H NMR spectra. The polymerization showed a first‐order kinetic characteristic and each of the obtained polymers had well‐controlled molecular weight and relatively low polydispersity index (PDI). Furthermore, the obtained end‐functionalized polystyrene (PS) in solution showed strong green‐light emission which is further affected by mixing different metal cations. In particular, the fluorescent intensity of the polymer was decreased in the presence of Ag⁺, Cu²⁺ and Fe³⁺.     

Improving the Alkaline Stability of Imidazolium Cations by Substitution

Imidazolium cations are promising candidates for preparing anion‐exchange membranes because of their good alkaline stability. Substitution of imidazolium cations is an efficient way to improve their alkaline stability. By combining density functional theory calculations with experimental results, it is found that the LUMO energy correlates with the alkaline stability of imidazolium cations. The results indicate that alkyl groups are the most suitable substituents for the N3 position of imidazolium cations, and the LUMO energies of alkyl‐substituted imidazolium cations depend on the electron‐donating effect and the hyperconjugation effect. Comparing 1,2‐dimethylimidazolium cations (1,2‐DMIm⁺) and 1,3‐dimethylimidazolium cations (1,3‐DMIm⁺) with the same substituents reveals that the hyperconjugation effect is more significant in influencing the LUMO energy of 1,3‐DMIms. This investigation reveals that LUMO energy is a helpful aid in predicting the alkaline stability of imidazolium cations.     

Simultaneous determination of chlorpyrifos and 3,5,6-trichloro-2-pyridinol in duck muscle by modified QuEChERS coupled to gas chromatography tandem mass spectrometry (GC-MS/MS)

A rapid, specific, and sensitive method based on modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) coupled to gas chromatography tandem mass spectrometry (GC-MS/MS) was developed and validated for simultaneous determination of chlorpyrifos (CP) and its metabolite 3,5,6-trichloro-2-pyridinol (TCP) in duck muscle. The residues of CP and TCP were extracted by acidified acetonitrile. The fat layer of the extract was removed under ?20 °C, then the organic layer was evaporated. The analytes were derivatized by N-(tert-butyldimethylsilyl)-N-methyltrifluoroacetamide (MTBSTFA) and cleaned up by a mixture of 150 mg MgSO₄, 25 mg graphitized carbon black (GCB), and 50 mg N-propylethylenediamine (PSA) to remove interference. The final extract was analyzed by GC-MS/MS. Recovery values at the spiking concentrations ranged from 86.2 to 92.3 % for CP and from 74.8 to 81.8 % for TCP, with relative standard deviations (RSDs) lower than 9.5 and 12.3, respectively. The correlation coefficients of CP (from 2 to 2,000 μg/kg) and TCP (from 1 to 1,000 μg/kg) were equal to or higher than 0.998. The limits of detection (LODs) were 0.3 and 0.15 μg/kg, and the limits of quantification (LOQs) were 1.0 and 0.5 μg/kg for CP and TCP in duck muscle, respectively. The average intra- and inter-day accuracy ranged from 84.6 to 91.2 % for CP and 75.6 to 82.3 % for TCP, and the intra- and inter-day precisions were from 5.8 to 8.2 % for CP and 6.5 to 11.9 % for TCP. Furthermore, the CP and TCP residues in duck muscle samples were detected for dietary risk assessment using the validated method.

纳米银对铕配合物荧光性质的影响(英文)

研究了纳米银对稀土铕-吡啶-2,6-二羧酸配合物(Eu(Ⅲ)C7H5NO4,Eu(Ⅲ)DPA)的荧光性质的影响。随着纳米银浓度增加,荧光强度先增强而后逐渐下降。较大粒径的纳米银使Eu(Ⅲ)DPA荧光增强效率较大,且达到最大荧光增强效率所需的纳米银浓度较低。在高浓度Eu(Ⅲ)DPA溶液体系中,纳米银导致荧光猝灭。电偶极子跃迁发射荧光增强效率大于磁偶极子跃迁发射荧光增强效率。分析认为,纳米银对Eu(Ⅲ)DPA荧光性质的影响与表面等离子体共振与激发态荧光中心强烈耦合以及表面等离子体再吸收有关。同时,纳米银对铕配合物的不对称率有影响,其影响因素与局域电磁场增强,折射率以及配位场有关。     

Semi-Preparative Scale Separation of Emodin from Plant Extract by Using Molecularly Imprinted Polymer as Stationary Phase

In this work, a core–shell molecularly imprinted polymer (MIP) was synthesized through sol–gel coating procedure by using silica beads, emodin, 3-aminopropyltriethoxysilane, tetraethoxysilane and tetrahydrofuran as supporting matrix, template, functional monomer, cross-linker and solvent, respectively. The selective recognition property for emodin and its analogues (physcion and aloe emodin) of the resultant MIP was evaluated in a chromatographic column for high-performance liquid chromatography (HPLC). The retention time and imprinted factor of MIP column for emodin, physcion and aloe emodin were 5.11, 0.63, 0.69 min and 4.69, 0.75, 1.38, respectively. It showed that the MIP beads had a good binding ability for emodin. Finally, one-step separation of emodin from alcohol extract of Rheum palmatum L. at semi-preparative scale was achieved and 380 mg of emodin was collected in 5 days. The product was characterized by mass spectrometry and HPLC and its purity was 95 %.