对称S-四嗪衍生物的合成及生物活性

用S粉作催化剂，以腈和水合肼为原料，用乙醇做溶剂在回流条件下直接合成了1，2-二氢-S-四嗪的衍生物，进而通过氧化得到对应的S-四嗪的衍生物，同时发现这些化合物具有一定的生物活性。     

均四嗪衍生物的合成

均四嗪衍生物在可见光区的最高吸收波长为500～550nm 之间,且由于其分子跃迁矩垂直于分子长轴,在液晶中显示负二向性,因而     

S-四嗪类高氮含能化合物的合成及表征

传统的有机含能化合物生成焓普遍较低,一般为负值或接近于零,所释放的能量主要来源于生成CO2和H2O的放热过程。四嗪类化合物是近年来国外研究较多的一类高氮化合物,其化学潜能主要来源于其正生成焓;同时分子结构中的高氮、低碳、氢含量不仅使其成气量大、燃烧产物少烟或无烟,而     

四嗪衍生物的合成及其抗癌性能研究

标题化合物是一类结构新颖,具有一定生物活性的新化合物(Ⅰ_1-7)。它由3,6-二甲基-1,6-二氢-1,2,4,5-四嗪(Ⅱ)在对二甲胺基吡啶(DMAP)催化下,与取代苯异氰酸酯(Ⅲ)反应生成。     

新型1,3-二取代酞嗪酮类衍生物的合成及抗肿瘤活性研究

为了寻找高效低毒的抗肿瘤药物,设计并合成新型的1,3位取代酞嗪酮类化合物.采用噻唑蓝(MTT)法对目标化合物在MCF-7(人乳腺癌细胞)、PC-3(人前列腺癌细胞)、SW-620(人结肠癌细胞)和HGC-27(人胃癌细胞)四种人类癌细胞的抗增殖活性进行评价.结果显示大部分化合物具有较好的抗增殖活性.其中,2-(4-(4-溴苯基)-1-氧代酞嗪-2(1H)-基)-N-(2-氟苯基)乙酰胺(5g)对MCF-7细胞的抗增殖活性较好,IC50值为6.01μmol/L,为抗肿瘤药物的研究提供了思路.     

具有除草活性的吡唑啉并四嗪酮衍生物的设计、合成与定量构效关系的研究

设计合成了一系列未见文献报道的4-乙氧羰基-1,7-二氢-1-取代苯基-5-(未)取代吡唑啉[5,1-d][1,2,3,5]四嗪-7-酮衍生物, 其结构均经过¹H NMR、IR和元素分析表征. 生测结果显示, 与已报道的化合物相比, 它们表现出较好的除草活性. 定量的结构与活性关系研究表明, 它们的除草活性与取代基的立体效应参数和疏水性参数呈现很好的相关性, 相关系数r大于0.8. 当作用对象为油菜时, 化合物的活性可能主要与取代基R¹的摩尔分子折射和取代基R²的疏水性参数有关. 当取代基R¹的摩尔分子折射参数为1.452时, 相应化合物可能具有对油菜最高的除草活性; 当作用对象为稗草时, 化合物的活性主要与取代基R²疏水性参数和Taft (Es)参数有关.     

四甲基吡嗪衍生物的合成及抗肿瘤活性研究

以四甲基吡嗪、2,4-二氯-5-硝基嘧啶和取代苯硼酸为原料,经过6步反应合成了4个未见文献报道的2-(取代苯基)-4-((3′,5′,6′-三甲基吡嗪-2′-基)甲氧基)-5-氨基嘧啶衍生物(5a～5d),其结构经~1HNMR、~(13)CNMR、HR-MS等方法表征。对反应条件进行了优化,使用CCK8试剂盒测定5a～5d对人神经母瘤细胞和肝癌细胞增殖的抑制作用,结果表明:化合物5c和5d对SH-SY5Y、Hep G2细胞均有一定的生长抑制活性。     

3，3’-偶氮-（6-氨基-1，2，4，5-四嗪）的合成与表征

以硝酸胍和水合肼为原料，经7步反应合成了高氮含能化合物3，3＇-偶氮-（6-氨基-1，2，4，5-四嗪），其结构经^1H NMR，^13C NMR，IR及元素分析表征。     

新型酞嗪酮-5-甲酰胺衍生物的合成及其抗癌活性

以糠醛为原料，依次与偏二甲基肼发生成腙反应、与马来酸酐发生D-A反应、芳环化、水解及与肼和取代苯肼反应得到呔嗪酮-5-羧酸，随后经酰胺化反应合成了17个新型的呔嗪酮-5-甲酰胺衍生物(6a~6g和9a~9j)，总收率21%~27%，其结构经¹H NMR, ¹³C NMR及HR-MS(ESI)表征。采用MTT法考察了化合物对人胰腺癌细胞(Capan 1)、人结直肠腺癌细胞(SW620)、人结肠癌细胞(HCT116)和人乳腺癌细胞(MDA-MB-231)的增殖抑制活性。结果表明：化合物9j对Capan-1细胞的增殖具有良好的抑制活性，IC₅₀为6.65 μM。     

芳酰基吡咯里嗪衍生物的设计与合成

COX和5-LOX双重抑制剂通过同时阻断炎症介质前列腺素和白三烯的形成, 产生协同的抗炎作用, 可以提高疗效, 同时避免COX抑制剂引发的副作用. 以芳基吡咯里嗪为先导物, 设计合成了2类15个5或6位芳酰基取代的7-芳基-2,3-二氢-1H-吡咯里嗪衍生物进行抗炎活性研究; 也可以其为模板进行结构修饰与优化, 设计合成更好的COX/5-LOX双重抑制剂. 同时分析了同分异构体III和IV的波谱学性质, 并确证了化合物的结构.     

GC-Q-TOF/MS快速筛查测定半夏中322种农药及化学污染物残留

利用GC-Q-TOF/MS检测技术,采用分散固相萃取(DSPE)样品前处理方法,建立了半夏中322种农药及化学污染物残留的筛查方法。探究了样品前处理过程中提取溶剂、缓冲盐体系、净化剂组成和用量对样品提取、净化等方面的影响,最终确定用1%的乙酸乙腈溶液和乙酸-乙酸钠缓冲体系进行提取,复合净化剂净化,GC-Q-TOF/MS测定的筛查方法。结果显示,322种农药及化学污染物中84.2%的化合物筛查限为5μg/kg,14.6%农药及化学污染物的筛查限为10μg/kg;在10,50,100μg/kg的添加水平下,农药及化学污染物的平均回收率分别为70.2%~119.5%,70.6%~119.8%,70.2%~119.9%,相对标准偏差(RSD)分别为0.2%~19.7%,0.2%~19.5%,0.5%~20.0%。与传统的分散固相萃取方法相比,该方法高效、快速,灵敏度高,准确性好,适用于半夏中322种农药及化学污染物残留的快速筛查和定量分析。     

热解吸低温等离子体质谱技术直接快速筛查蔬菜中的有机磷农药

在传统低温等离子体质谱技术的基础上引入热解吸装置,建立了一种直接快速筛查蔬菜中有机磷农药的新方法。白菜样品经乙腈提取,离心取上清液进行质谱检测,在正离子检测模式下,将承载样品的载玻片置于加热块上进行解吸,被低温等离子体射流离子化后进入质谱检测。结果表明,在优化实验条件下,8种有机磷农药在0.005～0.200 mg/L质量浓度范围内线性良好,相关系数均大于0.99,检出限为0.001～0.010 mg/L,加标回收率为90.5%～119%,相对标准偏差(RSD,n=6)为12%～17%。与无热解吸条件相比,检测灵敏度提高了9.3～41.7倍。该方法操作简单,无复杂的样品前处理,灵敏度高、准确性好,可用于蔬菜中8种有机磷农药残留的同时测定,在大批量样品的非靶向分析中有较大的应用前景。     

新型1,2,4-三唑硫醚取代乙酰胺类化合物的合成及抗菌活性

以3, 4, 5-三甲氧苯甲酸为原料,将具有优良生物活性的1,2,4-三唑与酰胺结构有机结合,通过酯化、肼解、环化、醚化、水解、缩合等反应合成1, 2, 4-三唑硫醚乙酰胺类化合物6a-6m,其结构经1H NMR,13C NMR,MS和元素分析进行了结构确证。初步生物活性测试表明：化合物浓度在50 μg/mL时,化合物6a-6m对猕猴桃软腐病中的葡萄座腔菌、拟茎点霉菌（Phomopsis sp.）和灰霉菌（B. cinerea）表现一定的抑制活性,其中化合物6k和6l对葡萄座腔菌、拟茎点霉菌和灰霉菌的抑制活性在83.4%至91.3 %;化合物6k对葡萄座腔菌和拟茎点霉菌的EC50值为46.6 μg/mL和30.8 μg/mL,均优于对照药剂嘧霉胺(57.6 μg/mL 和 32.1 μg/mL)。以上生物活性表明,1, 2, 4-三唑硫醚乙酰胺类化合物具有较好的抑菌活性,为进一步开发高活性化合物奠定一定基础。     

High-throughput Screening:Synthesis of a Novel Fluorescent Microspheres

As one of efficient analytes, fluorescent microspheres have shown much usability on many biochemical and biomedical processes. Recent applications with fluorescent microspheres have included cytokine quantitation, single nucleotide polymorphism genotyping, phosphorylated protein detection, and characterization of the molecular interaction of nuclear receptors. These,coupled with the rapid advances in molecular biology and synthesis techniques of drugs, have presented a basis for drug screening in a high-throughput format. Based on fluorescent microspheres,earlier assay formats of HTS relied mainly on proximity-dependent energy transfer including scintillation proximity assay (SPA) (Amersham Pharmacia Biotech) and FlashPlatesTM (NEN Life Science Products, Boston, MA). Indeed, drug screening-based such fluorescent emission is still accounting for about 20～50% of current content of high-throughput screening (HTS). Now, SPA is almost a standard technique in common HTS-lab. In literature, SPA microspheres is generally prepared from inorganic scintillators such as yttrium silicate and hydrophobic polymers such as polyvinyl toluene. However, in HTS research, such microspheres often show the disadvantages of strong hydrophobicity and low quantum efficiency. The strong hydrophobicity is mainly attributed to the hydrophobic monomer, vinyl toluene. The low quantum efficiency can be as a result of low transparence of the polymer, polyvinyl toluene. Thus, the subsequent treatments for such microspheres, so as coat a polyhydroxy film to decrease the hydrophobicity, are actually considerably complicated.It has been well known that poly(methyl methacrylate) (PMMA), a good biocompatible polymer with not only adequate mechanical strength but also excellent transparence, can be regarded as an ideal candidate material for fluorescent matrix. In present study, methyl methacrylate as monomer and 2,5-diphenyloxazole (DPO) as fluorescent dye were used to the fluorescent microspheres. In guaranteeing the hydrophilicity of microsphere surfaces, dispersion polymerization was in common use (stabilizer, Polyvinyl pyrrolidone). As is apparent, with such a method in hand, one would normally find that almost no subsequent treatment for microspheres can be involved. Also such a novel fluorescent microspheres is a more suitable and the method used in present research is more practical method in comparison to common method. As the original work, the purposes of this article are to synthesize such fluorescent microspheres and probe the probable roles of synthesis conditions on microsphere synthesis. The effects of stabilizers, initiators, dispersion mediums, monomer content, and reaction temperature on the synthesis process and the particle size, as well as its panicle distribution have been shown. Also the probable role of fluorescent dye in the polymerization has been thermodynamicaily discussed.     

毛细管气相色谱法测定热不稳定有机磷农药辛硫磷

The thermo-labile organophosphorous pesticide Phoxim was determined by capillary gas chromatographywith flame phototnetric detector. When high linear velocity H_2(>200cm/s) was used as carrier gas,the thermo-decomposition of Phoxim was considerably reduced.The most important gas chromatography conditions,injectortempereture and column head pressure,were studied.The thermo-decomposition preducts were identified by gaschromatography-mass spectrometry.     

气相色谱-电子捕获检测器同时测定茶叶中有机氯及拟除虫菊酯类农药残留

在超声波辅助下,以正己烷-二氯甲烷（1：1,V／V）混合溶剂提取样品,提取液用弗罗里硅土和中性氧化铝混合柱净化,用气相色谱-电子捕获检测器（GC-ECD）同时测定茶叶中18种有机氯和9种拟除虫菊酯类农药残留。有机氯农药在0.001-0.2μg／mL,拟除虫菊酯类农药在0.005-1.0μg／mL范围内线性良好。有机氯农药在0.04、0.01μg／mL两个添加水平的回收率分别为89.5％-113.2％和80.0％-112.7％,相对标准偏差分别为3.82％-9.64％和5.32％-13.8％。拟除虫菊酯在0.2、O.05μg／mL两个添加水平的回收率分别为97.5％-129.6％和87.3％-110.2％,相对标准偏差分别为3.78％-10.72％和3.02％-13.84％。本方法快速、灵敏、准确、可靠,用于江西茶叶样品中有机农药残留测定,获得较好结果。     

Mesoporous Bimetallic PtPd Nanoflowers as a Platform to Enhance Electrocatalytic Activity of Acetylcholinesterase for Organophosphate Pesticide Detection

Mesoporous bimetallic PtPd nanoflowers (MPtPdN) were synthesized by a surfactant‐directing method. The MPtPdN was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and wide‐angle X‐ray diffraction (XRD). The use of MPtPdN as a platform for the indirect electrochemical detection of organophosphate pesticides (OPs) via enzymatic inhibition pathway was demonstrated. Due to the nanostructure of MPtPdN and the synergy effect of the noble metal nanoparticles, a novel and sensitive acetylcholinesterase (AChE) biosensor for OPs detections based on MPtPdN and enzyme inhibition was prepared. The inhibition of omethoate exhibited a linear relationship from 4.7×10⁻¹¹ to 4.7×10⁻⁸ M with a detection limit of 1.7×10⁻¹² M (S/N=3). The proposed AChE biosensor was reliable and can be used to measure the concentration of omethoate in different spiked samples with high accuracy and satisfactory recovery. The preparation of biosensors based on the MPtPdN can be further extended to construct many other important enzyme biosensors.     

镧系盐催化合成辣椒酯衍生物研究

对比研究了三氯化铕,三氯化镧,三氯化铈和三氯化镨四种镧系盐催化剂化学选择酯化香草醇收率的影响。以三氯化镧为化学选择催化剂,且香草醇与三氯化镧物质的量比为1：0.005时,癸酸香草醇酯的收率最高为85%,并用该法合成辛酸香草醇酯和月桂酸香草醇酯,其收率分别为87%和71%。     

Histidine‐Containing Peptide Catalysts Developed by a Facile Library Screening Method

Although peptide catalysts have a high potential for the use as organocatalysts, the optimization of peptide sequences is laborious and time‐consuming. To address this issue, a facile screening method for finding efficient aminocatalysts from a peptide library has been developed. In the screening for the Michael addition of a malonate to an enal, a dye‐labeled product is immobilized on resin‐bound peptides through reductive amination to visualize active catalysts. This procedure allows for the monitoring of the reactivity of entire peptides without modifying the resin beads beforehand. Peptides containing histidine at an appropriate position were identified by this method. A novel function of the histidyl residue, which enhances the binding of a substrate to the catalyst by capturing an iminium intermediate, was indicated.     

Synthesis, Crystal Structure Analysis and DFT Calculation of 1-Benzoyl-3,6-diphenyl-1,4-dihydro-1,2,4,5-tetrazine

The new title compound, 1-benzoyl-3,6-diphenyl-1,4-dihydro-1,2,4,5-tetrazine (C21H16N4O, Mr = 340.38), has been prepared and its crystal structure can not be confirmed by the results of MS, elemental analysis, IR spectrum and 1H NMR spectrum, but determined by X-ray diffraction. The title compound crystallizes in an orthorhombic space group P212121 with a = 7.1100(19), b = 12.115(3), c = 19.884(6), V = 1712.7(8)3, Z = 4, Dc = 1.320 g/cm3, F(000) = 712, μ = 0.085 mm-1, MoKa radiation (λ = 0.71073), R = 0.0334 and wR = 0.0845 for 2254 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the central tetrazine adopts an unsymmetrical boat conformation. According to the bond lengths of tetrazine ring, the molecule should be 1,4-dihydro-1,2,4,5-tetrazine, rather than 1,2-dihydro-1,2,4,5-tetrazine. The crystal structure is stabilized mainly by intermolecular N–H···O hydrogen bonds.