Molecularly imprinted polymers (MIPs) are widely used in immunoassays as biomimetic receptors. MIPs are prepared by different polymerization methods and result in diverse performance in these assays. In this paper, MIPs were prepared via bulk polymerization, precipitation polymerization and a surface polymerization, which is newly developed by our group, to compare their performances in a biomimetic fluoroimmunosorbent assays. The imprinted polymers were prepared using the herbicide, 2,4-dichlorophenoxyacetic acid (2,4-D) as the template, 4-vinylpyndine and ethylene glycol dimethacrylate as the functional and crosslinking monomer respectively by thermal polymerization. A novel fluorescent derivative of 2,4-D was synthesized from 9-anthracenemethanol to compete the binding sites of the MIPs with 2,4-D. The results show that the polymer coating provides the largest concentration range and the most facile format for the competitive immunoassay. The sandwich method can be used to produce very stable and reusable polymer coating which is expected to replace polymer particles in immunoassays.

Novel dansyl chloride-based fluorescent polymer-coated chips (PCFCs) were designed and developed via polymerization of 2-(5-(dimethylamino) naphthalen-1-ylsulfonyloxy)ethyl methacrylate (DNS-EMA) on the surface of a 3-(trimethoxysilyl)propyl methacrylate (MPS) modified glass slide with a supporting membrane. The chemical linkage of DNS-EMA on PCFC surface was verified by H-1-NMR, IR, and fluorescence measurements. Particularly, the optimized fluorescent polymer-coated chip (PCFC6) in 1/1 (v/v) acetonitrile /water exhibited higher sensitivity toward Hg2+ than the other tested metal ions at concentrations ranging from 1.66 mu mol/L to 50.6 mu mol/L with R-2=0.9923. Interestingly, PCFC6 is water-compatible, photostable and exhibits good selectivity to Hg2+ even at low concentrations compared to other representative metal cations with 89.2-109.9 % recoveries.

AIM:To develop anti-cancer active pharmaceutical intermediates.BACKGROUND:Acridone derivatives possess a wide range of pharmacological activities: 1) they intercalate DNA and 2) form a covalent bond with DNA.OBJECTIVE:To screen in vitro anti-cancer activity against Cdc25b and SHP1 of new acridone derivatives and preliminary study on the structure-activity relationship.MATERIALS AND METHODS:The synthesis of new acridone derivatives and in vitro evaluation of their anti-cancer activity on Cdc25b and SHP1 was achieved. Natural products that contain acridine structures, such as cystodytin A and acronycine, are isolated from certain marine (tunicates & ascidians, sponges, sea anemones) and plant (bark of Australian scrub ash tree) species. Herein, we report the efficient one-pot green synthesis of twelve novel 3,4-dihydro-1 (2H) acridone derivatives, using montmorillonite K10 as the catalyst and iron/citric acid in water. Also, their inhibitory activity against Cdc25B and SHP1 is examined, in which specific derivatives show enhanced inhibitory activity compared to others.RESULTS AND DISCUSSION:Twelve new acridone derivatives were prepared, starting from 2-nitrobenzaldehyde derivatives and 1, 3-cyclohexanedione derivatives, which exhibited substantial anti-cancer activity against Cdc25b and SHP1 cells.CONCLUSION:Preliminary studies on the structure-activity relationship have shown the influence of the structural parameters and, in particular, the nature of the substituent on aromatic ring structure and cyclohexanone. Other: Further study on the structure-activity relationship is required.

In this work, two quinoxline type monomers, 10,14-bis(4-octyl-2-thienyl)-dipyrido[3,2-a:2′,3′-c] [1, 2, 5] thiadiazolo[3,4-i] quinoxaline (OTPTP) and 10,14-bis(4-octyl-2-thienyl)-dibenzo[a, c][1,2,5]thiadiazolo [3,4-i] quinoxaline (OTBTP) were prepared, and the electrochromic features of their polymer films that were synthesized on the ITO glass surface by electrochemical polymerization were studied. The electronic characteristics of two different electron-withdrawing groups and their influences on the electrochemical polymerization of monomers and electrochromic performance of the obtained polymers were observed. The electronic performance of monomers illustrated that OTBTP can be polymerized in the lower potential range than OTPTP due to the stronger electron-withdrawing capability of the electron-withdrawing groups in OTPTP which contains two dipyridine units. The UV Visible NIR spectra analysis showed that both polymers, POTPTP and POTBTP, have one broad absorbance band in the region of 400 ~ 1600 nm at the neutral state. The electrochromic analysis revealed that the two polymer films exhibited reasonable optical contrasts in the infrared region of 1000 ~ 1600 nm with low response time (about 5 s) and low band gap.

Borondipyrromethene (BODIPY) dyes have attracted enormous interest due to their excellent photo-physical and chemical properties. However, the strong hydrophobic nature of the dyes limits their applications in water based biological and medical samples. In this work, BODIPY derivatives bearing vinyl group were synthesized and polymerized to obtain high dispersible nanoparticles. The BODIPY monomers were synthesized via esterification of their phenol groups with acryloyl chlorides and fully characterized by NMR, MS, UV-vis, and fluorescence spectroscopies. BODIPY fluorescent polymer nanoparticles were prepared using precipitation polymerization of the BODIPY monomers with methacrylic acid (MAA) in the presence of cross-linkers and characterized in respect to spectroscopic property, polymer morphology and particles size distribution. It was found that the type of cross-linker and amount of solvent have significant effect on particles size and morphology. A prominent necklace-like structure that enabled the polymer nanoparticles to have a good dispersibility could be obtained by using trimethylolpropane trimethacrylate/divinylbenzene (TRIM/DVB) as the cross-linker. Moreover, the BODIPY based polymers exhibited much stronger fluorescence than BODIPY monomer in aqueous solution, especially with the smaller nanoparticles. The fluorescent polymer nanoparticle preparation proposed in this study can be a good choice for addressing the limitation of hydrophobic BODIPY dyes applications in the water-based biomedical media.

A straightforward and convenient route has been developed for the synthesis of 3‐unsubstituted phthalide derivatives from aryl amides and paraformaldehyde by ruthenium(II)‐catalyzed C–H activation. The reaction proceeds through tandem ortho‐hydroxymethylation of aryl amide and subsequent intramolecular lactonization.

Fluorescent immunosorbent assay (FIA) is very promising for sensitive and selective analysis in bio-medical applications. Here, we proposed an assay, using fluorescent engineering of analytes and the corresponding molecularly imprinted polymers (MIPs) as a plastic antibody. Three drug molecules (metronidazole, zidovudine and lamivudine) were condensed with 9-aminoacridine, using succinic anhydride as a spacer. The target products were characterized with 1H-NMR, IR and mass spectrometry. UV-vis absorption and fluorescent properties of the fluorophore-labeled drug molecules were investigated. Feasibility of the fluorescent biomimetic immunosorbent assay based on MIPs was demonstrated in the solution. This work will provide sound foundation for the future application in real sample.

Nitrogen-doping in carbon materials is a common strategy to enhance electrochemical capacitance. Most studies focused on the application of N-doped materials. However, the evolution of nitrogen in the materials and the effect of nitrogen content of materials on capacitance is rarely discussed. In this study, we use low molecular weight hydrogel as a precursor, doped with different amount of urea to change nitrogen content. We discovered that the nitrogen-doping may change the morphology of the materials after pyrolysis. We further analyzed the electrochemical properties of the N-doped porous carbon materials. The electrochemical capacitance may increase due to nitrogen-doping, but with high nitrogen content, the capacitance decreased conversely. The increase of electrochemical capacitance may relate to the content of quaternary nitrogen.

Due to the special functional structural units and important applications in many fields, the study of acridine derivatives has become a hot topic worldwide. The large conjugated ring enables these dyes to be markers for fluorescence and im-aging. Thanks to the ability of embedding into DNA chain, they have a wide range of applications in medicine and other fields. These dyes have the very similar color index value to that of the natural compounds. As an alternative to metal semiconductor material, acridines have presented potential value in the field of organic semiconductor materials. In recent years, emerging of the new and simple preparation technique, such as microwave assisted synthesis, metal free catalysis, one pot synthesis, and so on, has brought more attention to the synthesis and application of acridines. In this paper, various synthetic methods of acridine derivatives since 2010 and their applications in medicine, fluorescent materials, industrial dyeing materials and electrolumi-nescence are introduced. The work about acridines accomplished in our group is also introduced. In the end, the future pro-spective of synthesis and application of acridine derivatives is proposed.

Spiroisoxazoline compounds have so extensive biological activity that they are important drug intermediates,and they are also important organic synthetic intermediates.The relevant reports for forty years are reviewed in this paper.On the basis of reaction mechanisms,the synthetic methods of spiroisoxazoline compounds are classified into the following five types:oxidation,intramolecular condensation,nucleophilic addition,1,3-dipolar cycloaddition,and other methods.Among them,the most widely used method is 1,3-dipolar cycloadditio.This method is of simple operation,high yield and good stereoselectivity,but one of its synthons-carbon dipolarophiles is not easy to get,and generally goes through many steps of reaction to prepare.In addition,their biological activities are summarized as six categories:the activity of inhibiting the growth of the larvae,the activity of slowing hardening of the arteries,the activity for the treatment of pain,the activity of lowering blood sugar,the anticancer activity and the antibacterial activity.

从蘑菇中提取的活性物质捕蝇蕈（muscimol）、环丝氨酰（cycloserin）和鹅膏蕈氨酸（ibotenic acid）都含有异噁唑药效团结构,本文以捕蝇蕈（蕈毒碱）为结构模型,采用分子重组法,通过1,3-偶极环加成反应,合成了3-（1’,2’-二-O-异亚丙基二氧乙基）-5-芳基-3a,6a-二氢-4,6-二氧代氮杂茂并[3’,4’-d]异噁唑啉的蕈毒碱类似物,其结构经UV-Vis、1H NMR、IR和元素分析进行了表征。对合成的化合物进行了体外药物活性筛选,发现结构中的药效团作为潜在的非共价DNA结合体,显示了不同程度的抗癌、抗炎及免疫性疾病活性。初步体外抗癌活性结果表明,当样品浓度为20μg·m L -1 时,化合物3a~3o对细胞分裂周期25B磷酸酯酶（Cdc25B）的抑制率为56.99%~99.94%,甚至当样品浓度为5μg·m L -1 时,除了3f、3h、3i、3m、3o无活性外,其余化合物的抑制率仍为66.85%~99.84%,值得进一步研究。此外,体外白细胞共同抗原（CD45）活性实验结果表明,当样品浓度为20μg·m L -1 时,除了3i无活性外,其余化合物对白细胞共同抗原CD45蛋白酪氨酸磷酸酶A具有良好的抑制活性,其抑制率为63.08%~92.09%。这些具有活性的目标化合物是潜在的Cdc25B和CD45蛋白酪氨酸磷酸酶A抑制剂,在癌症、炎性及免疫性疾病治疗方面具有很好的应用前景。

The new spiro compound 1-carbonyl-3-methoxy-2,4-diene-spiro[5,7]-14,15-dihydroxynaphthalene ( 1 ) and four known compounds [calycosin ( 2 ), psoracinol ( 3 ), octadecyl caffeate ( 4 ), (–)-syringaresinol ( 5 )] were isolated from the aerial part of Caragana acanthophylla. The molecular structures were determined using PMR, 13 C NMR, 2D, and mass spectra.

Fouteen 2-methyl-3-ethylcarboxy-5-aryl-3a, 6a-dihydro-4,6-dioxopyrrolino[3',4'-d]-isoxazoliniumtetrachloroferrate derivatives 2a similar to 2g and 2-methyl-3-carboxyl-5-aryl-3a, 6a-dihydro-4,6-dioxopyrrolino[3', 4'-d]-isoxazolinium-tetrachloroferrate derivatives 4a similar to 4g were synthesized by using dimethylsulfate as a N-methylating reagent and ferric(III)-chloride as anion exchange reagent in hydrochloric acid. The structures of the target compounds 2 and 4 were characterized by H-1 NMR, IR spectra and elemental analysis. The preliminary in vitro anticancer activity on the compounds showed that most compounds possess anti-cancer activity at some extent. At the test concentration of 20 mu g/mL, compounds 2a similar to 2g and 4a similar to 4g showed inhibition activities in the range of 97.32%similar to 99.94% and 97.45%similar to 99.92% against cell division cycle 25B phosphatase (Cdc25B), respectively. At the test concentration of 20 mu g/mL, compounds 2a similar to 2g and 4d similar to 4g showed inhibition activities in the range of 52.18%similar to 97.15% and 86.66%similar to 99.45% against SH2-containing proteintyrosinephosphatase-1 (SHP1), respectively. Compounds 4a similar to 4c only have the inhibition activities in the range of 15.21%similar to 47.11%, which is lower than IC50 against SHP1. Preliminary discussion was carried out on the structure-activity relationship of the target compounds.

In this paper, 1-aryl-3-substituted-4-(9-acridinyl)azetidin-2-one derivatives L1 similar to L6 and 2-(9-acridinyl)-3-aryl-1,3-thiazolidin-4-one derivatives T1 similar to T3 were synthesized through [2+2] cycloaddition reaction and cyclocondensation reaction of N-(p-substitutedaryl)-C-(9-acridinyl)formaldimines Schiff base with ketene, which in situ generated from chloroacetyl chloride and benzyloxyacetyl chloride in the presence of triethylamine, and mercaptoacetic acid. The synthesized compounds have also been screened in vitro anticancer activities and the leukocyte common antigen activities. The results showed that the inhibitory activity of compound L4 is 79.4% on human tumor cell HL-60 (Leucocythemia), at the test concentration of 10 mu mol/L. The inhibitory activities of compounds L5, L6 and T3 on Cdc25B (Cell division cycle 25B) phosphatase are 80.64%, 99.75% and 99.34% at the test concentration of 20 mu g/mL, respectively. The inhibitory activities of compounds L6 and T3 on CD45 (leukocyte common antigen, LCA) protein tyrosine phosphatase A are 86.12% and 91.03% at the test concentration of 20 mu mol/mL, respectively. The structure-activity relationship of these compounds was investigated on the bases of bioassay experimental results of these compounds.

Fifteen novel 2-methyl-3-(1',2'-O-cyclohexylidendioxyethyl)-5-aryl-3a,6a-dihydro-4,6-dioxopyrrolino[3',4'-d]-isoxazolinium-tetrachloroferrate derivatives 4a similar to 4o were synthesized by N-methylation of the corresponding isoxazoline using dimethyl sulfate as a methylating reagent and ferric(III)-chloride as anion exchange reagent in hydrochloric acid. The structures of the target compounds 4a similar to 4o were characterized by H-1 NMR, IR spectra and elemental analysis. The preliminary in vitro bioassay on the compounds showed that most compounds possess anti-cancer activity and the Leukocyte common antigen activity at some extent. At the test concentration of 20 mu g/mL, all compounds showed inhibition activity of >= 97.55% against Cdc25B (cell division cycle 25B) phosphatase except for compound 4h, and inhibition activity of 68.41%similar to 93.38% against leukocyte common antigen (LCK) CD45 protein tyrosine phosphatase A, respectively. Preliminary discussion was carried out on the structure-activity relationship of the target compounds.

Fifteen 3-(1', 2'-di-O-cyclohexylidendioxyethyl)-5-aryl-3a, 6a-dihydro-4, 6-dioxo-pyrrolino[3', 4'-d] isoxazoline derivatives (3a-3o) were synthesized by 1, 3-dipolar cycloaddition reaction of N-arylmaleimides and the nitrile oxide in situ generated from 2, 3-O-cyclohexylidene-D-glycerohydroximoyl chloride, in the presence of triethylamine. The structures of the target compounds 3a-3o were characterized by 1H NMR, IR and elemental analysis. The preliminary bioassay on the compounds showed that some compounds possess in vitro anticancer activity and the leukocyte common antigen activity to a different extent. The compounds 3e, 3h, 3j and 31 showed Cdc25A phosphatase inhibitory activity of 60.6%, 58.6%, 51.4% and 98.4% respectively at the test concentration of 20 microg x mL(-1), and among them 31 had inhibition rate of 86.97% even at the concentration as low as 5 microg x mL(-1), indicating worthy to be future studied. The compounds 3e, 31 and 3n showed an inhibitory activity of 57.7%, 74.4% and 77.3% on CD45 protein tyrosine phosphatase A, respectively, at the test concentration of 20 micromol x mL(-1). The structure-activity relationship of 3-(1', 2'-di-O-cyclohexylidendioxyethyl)-5-aryl-3a, 6a- dihydro-4, 6-dioxo-pyrrolino[3', 4'-d]isoxazoline derivatives was also discussed.

利用芳胺的N-烷基化反应,混酸硝化,硝基还原等原理合成了N’-2,6-二甲基苯基-N,N-二乙基乙二胺及其衍生物,利用IR光谱和1H NMR测试技术对化合物进行了表征。对所合成的化合物和原料进行了吸收和荧光光谱的测定及分析,探讨了化合物的结构与光谱之间的关系。探索了在酸碱等条件下荧光光谱的变化规律。

Lidocaine hydrochloride is widely used as a local anesthetic and arrhythmia drug.This article reviewed determination of lidocaine hydrochloride in pharmaceutical preparations and pretreatment as well as determination of biological samples such as serum and plasma with efficient thin-layer chromatography,high performance liquid chromatography and micellar electrokinetic capillary electrophoresis,providing reference for future research.