双水杨醛类缩乙二胺席夫碱的合成及光谱性能

以水杨醛为原料,通过硝化或溴化反应合成了3,5—二硝基水杨醛(p.m57℃～59℃),5—溴水杨醛((m.p104℃～105℃),3—硝基水杨醛(m.p124℃～127℃),和3—溴—5—硝基水杨醛(m.p148℃～149℃)收率分别为76.0%、81.8%、63.0%和80.5%用水杨醛及其衍生物同乙二胺反应制备出11种双水杨醛缩乙二胺席夫碱。采用~1H—NMR对合成的系列席夫碱进行了表征,通过紫外光谱测定席夫碱中苯环上不同取代基对紫外吸收波长的影响。     

5-溴水杨醛席夫碱镍配合物修饰碳糊电极的制作

以5-溴水杨醛为原料,制备了5-溴水杨醛席夫碱镍配合物,制作了5-溴水杨醛席夫碱镍配合物修饰碳糊电极,确定了电极制作的晟佳材料配比:活性物质质量:石墨质量:固体石蜡质量为9.43%:56.60%:33.96%.     

2-(2-羟基-4-溴苯基)-5,6-二硝基苯并咪唑的合成

以4,5-二硝基邻苯二胺和5-溴水杨醛反应,控制不同条件,可分别得到单Schiff碱化合物5-溴水杨醛缩4,5-二硝基邻苯二胺和苯并咪唑衍生物2-(2-羟基-4-溴苯基)-5,6-二硝基苯并咪唑,前者在一定的条件下能够关环转化为后者,对它们的结构进行了UV-Vis、IR、1HNMR、MS表征,对构形转化的反应机理进行了研究.     

新型多溴代水杨醛及其Schiff碱配体的合成与表征

以芳基硼酸和3-溴-5-叔丁基水杨醛为原料,经Suzuki偶联反应分别得到3-苯基-5-叔丁基水杨醛和3-(4-甲基苯基)-5-叔丁基水杨醛。3-苯基-5-叔丁基水杨醛在溴化反应时,发现不同温度下反应结果不同:分别生成一溴代产物3-(4-溴苯基)-5-叔丁基水杨醛和二溴代产物3-(4-溴苯基)-5-溴水杨醛。在50℃下,3-(4-甲基苯基)-5-叔丁基水杨醛经溴化得到三溴代产物3-(4-甲基-3,5-二溴苯基)-5-溴水杨醛,再经过与(S)-缬氨醇缩合后得到手性Schiff碱配体。通过红外、高分辨质谱、核磁共振等手段对其结构进行了表征。     

双-(5-溴水杨醛)缩邻苯二胺双席夫碱的合成研究

以邻苯二胺和5-溴水杨醛为原料,合成了新化合物双-(5-溴水杨醛)缩邻苯二胺双席夫碱,应用元素分析、红外光谱和紫外光谱进行了表征。探讨了合成反应的影响因素,找出了合成的最佳条件。产品的收率为52.2%。     

1-(5-萘酚7-磺酸)-3-[4-(苯基偶氮)苯基]-三氮烯-溴化十四烷基吡啶- 阴离子表面活性剂显色反应研究

介绍了在NaOH介质中，阳离子表面活性剂溴化十四烷基吡啶(TPB)存在下，1—(5—萘酚—7—磺酸)—3—[4—(苯基偶氮)苯基]—三氮烯(NASAPAPT)与阴离子表面活性剂(AS)的显色反应。该显色反应显色快，稳定，显色配合物最大吸收位于594nm，显色剂与阴离子表面活性剂配合比为1：3。研究的方法用于实样分析。     

烟酰肼-5-溴水杨醛与镁金属配合物的合成与表征

以乙醇作溶剂,合成了5-溴水杨醛烟酰腙配体化合物,同时制备了5-溴水杨醛烟酰腙与Mg（Ⅱ）的金属配合物。利用元素分析、红外光谱、紫外光谱法对配体及配合物进行了表征,并对配体和配合物的荧光性质进行了初步研究。     

5-氨基间苯二甲酸缩水杨醛席夫碱的合成研究

以5-氨基间苯二甲酸为原料,分别与含不同卤素取代基的5-溴水杨醛、3,5-二氯水杨醛和邻香草醛反应合成了3种新的含不同取代基的5-氨基间苯二甲酸缩水杨醛席夫碱,通过元素分析、IR和~1H NMR对结构进行表征。运用正交实验得到合成5-氨基间苯二甲酸缩5-溴水杨醛席夫碱的最佳工艺条件:胺醛摩尔比为1∶1.2,反应时间为6 h,催化剂冰乙酸用量为1.0 mL,产率达79%。     

3,5-二溴水杨醛的合成

以水杨醛及取代水杨醛为原料,在环境友好介质聚乙二醇400(PEG-400)中,N-溴代丁二酰亚胺(NBS)为溴化试剂于超声波条件下高收率的合成了3,5-二溴水杨醛。     

5-溴水杨醛烟酰腙与镁金属配合物的合成与表征

以乙醇为溶剂,合成了5-溴水杨醛烟酰腙配体化合物,同时制备了5-溴水杨醛烟酰腙合Mg(II)金属配合物。利用元素分析、红外光谱、紫外光谱法对配体及配合物进行了表征,并对其荧光性质进行了初步研究。     

Nonenzymatic ligation of short-chained 2'-5'- or 3'-5'-linked oligoribonucleotides on 2'-5'- or 3'-5'-linked complementary templates

5'-pACUG tetraribonucleotides containing 2'-5' or 3'-5' linkages self-condensed on 2'-5'- or 3'-5'-linked complementary decaribonucleotide (5'-CAGUCAGUCA) templates. CD and UV melting studies showed that helix formation took place in all four possible combinations of linkage isomers of the substrate tetramer and the template decamer under the ligation conditions. The hybridization ability followed the order: [3'-5' tetramer with 3'-5' decamer] > [2'-5' tetramer with 3'-5' decamer] > [2'-5' tetramer with 2'-5' decamer] > or = [3'-5' tetramer with 2'-5' decamer]. Each tetramer condensed on the complementary decaribonucletide template to form the corresponding octamer, but the ligation efficiency varied considerably, depending on the types of linkage in the tetramer substrate and the template decamer. The yields of the octamers obtained by the template-directed ligation followed the order: [2'-5' substrate: 2'-5' template] > [3'-5':3'-5'] > [2'-5':3'-5'] > [3'-5':2'-5']. The results demonstrate that a homo-linkage system is preferable for the template-directed synthesis of RNA. The resulting linkage of the octamer formed from the 2'-5'-linked substrate and the 2'-5'-linked template is mainly 2'-5'.     

MiR-181a-5p Regulates NIS Expression in Papillary Thyroid Carcinoma

NIS is a potent iodide transporter encoded by the SLC5A5 gene. Its expression is reduced in papillary thyroid carcinoma (PTC). In this study we analyzed the impact of miR-181a-5p on NIS expression in the context of PTC. We used real-time PCR to analyze the expression of SLC5A5 and miR-181a-5p in 49 PTC/normal tissue pairs. Luciferase assays and mutagenesis were performed to confirm direct binding of miR-181a-5p to the 3′UTR of SLC5A5 and identify the binding site. The impact of modulation of miR-181a-5p using appropriate plasmids on endogenous NIS and radioactive iodine accumulation was verified. We confirmed downregulation of SLC5A5 and concomitant upregulation of miR-181a-5p in PTC. Broadly used algorithms did not predict the binding site of miR-181a-5p in 3′UTR of SLC5A5, but we identified and confirmed the binding site through mutagenesis using luciferase assays. In MCF7 and HEK293-flhNIS cell lines, transfection with mir-181a-expressing plasmid decreased endogenous SLC5A5, whereas silencing of miR-181a-5p increased it. We observed similar tendencies in protein expression and radioactive iodine accumulation. This study shows for the first time that miR-181a-5p directly regulates SLC5A5 expression in the context of PTC and may decrease efficacy of radioiodine treatment. Accordingly, miR-181a-5p may serve as an emerging target to enhance the efficacy of radioactive iodine therapy.     

丙型肝炎病毒NS5B全长基因及截短形式基因的克隆、表达及鉴定

目的构建丙型肝炎病毒(HCV)NS5B-FL、NS5B-C21和NS5B-C51重组原核表达载体,并进行目的蛋白的表达及鉴定。方法利用PCR技术扩增3种长度的NS5B基因,经BamHI和XhoI双酶切后连接到经同样酶切的原核表达载体pET-28a(+)上,转化大肠杆菌BL21(DE3),IPTG诱导表达重组蛋白,并进行纯化及鉴定。结果所构建的3种重组质粒pET-28a(+)-NS5B-FL、pET-28a(+)-NS5B-C21和pET-28a(+)-NS5B-C51,转化大肠杆菌BL21(DE3)后,经PCR及酶切鉴定,均能扩增或酶切出相应大小的目的基因片段,表达的6His-NS5B-FL融合蛋白主要以包涵体形式存在,而表达的6His-NS5B-C21和6His-NS5B-C51融合蛋白的可溶性明显增加。纯化的6His-NS5B-C21蛋白未发生降解,6His-NS5B-FL和6His-NS5B-C51蛋白发生了部分降解。纯化后的3种蛋白均能与丙肝患者血清发生反应。结论已成功构建了3种NS5B基因的重组表达载体,并获得了目的蛋白表达,为进一步抗HCV药物的筛选奠定基础。     

5-Hydroxytryptophan (5-HTP): Natural Occurrence,Analysis, Biosynthesis,Biotechnology, Physiology and Toxicology

L-5-hydroxytryptophan (5-HTP) is both a drug and a natural component of some dietary supplements. 5-HTP is produced from tryptophan by tryptophan hydroxylase (TPH), which is present in two isoforms (TPH1 and TPH2). Decarboxylation of 5-HTP yields serotonin (5-hydroxytryptamine, 5-HT) that is further transformed to melatonin (N-acetyl-5-methoxytryptamine). 5-HTP plays a major role both in neurologic and metabolic diseases and its synthesis from tryptophan represents the limiting step in serotonin and melatonin biosynthesis. In this review, after an look at the main natural sources of 5-HTP, the chemical analysis and synthesis, biosynthesis and microbial production of 5-HTP by molecular engineering will be described. The physiological effects of 5-HTP are discussed in both animal studies and human clinical trials. The physiological role of 5-HTP in the treatment of depression, anxiety, panic, sleep disorders, obesity, myoclonus and serotonin syndrome are also discussed. 5-HTP toxicity and the occurrence of toxic impurities present in tryptophan and 5-HTP preparations are also discussed.     

过渡金属改性HZSM-5催化剂的乳酸乙酯脱水性能

分别采用FeCl3·6H2O和MnCl2·4H2O对HzsM-5分子筛进行改性,得到Fe-ZSM-5和Mn-ZsM-5催化剂,采用x射线衍射(xRD)和傅立叶红外光谱(FT-IR)对改性前后的样品进行表征,并考察了HZSM-5分子筛改性前后在乳酸乙酯脱水制丙烯酸乙酯反应中的催化性能.结果表明,与HZSM-5相比,改性后的Fe-ZSM-5和Mn-ZSM-5的结晶度下降,硅铝比降低,活性降低,选择性增加,且Mn-ZSM-5的催化性能优于Fe-ZSM-5的催化性能,在180℃下反应3 h,丙烯酸乙酯收率达到14.65%.     

Terpendole E and its Derivative Inhibit STLC‐ and GSK‐1‐Resistant Eg5

Terpendole E is first natural product found to inhibit mitotic kinesin Eg5, but its inhibitory mechanism remains to be revealed. Here, we report the effects of terpendole E and 11ketopaspaline (a new natural terpendole E analogue) on the Eg5–microtubule interaction and in several Eg5 mutants. 11‐Ketopaspaline is a shunt product from terpendole E, and it shows potent inhibitory activity against the microtubule‐stimulated ATPase activity of Eg5. Unlike other Eg5 inhibitors, such as S‐trityl‐L ‐cysteine (STLC) and GSK‐1, both terpendole E and 11‐ketopaspaline only partially inhibited Eg5–microtubule interaction. Furthermore, terpendole E and 11‐ketopaspaline inhibited several Eg5 mutants that are resistant to STLC (Eg5^D130A, Eg5^L214A) or GSK‐1 (Eg5^I299F, Eg5^A356T), but with the same extent of inhibition against wild‐type Eg5. Because Eg5^D130A and Eg5^L214A show cross‐resistance to most known Eg5 inhibitors, which bind the L5 loop, these results suggest that terpendole E and its analogues have a different binding site and/or inhibitory mechanism to those for L5 loop‐binding type Eg5 inhibitors.     

Synthesis of Fe,Co, and Mn substituted AlPO-5 molecular sieves and their catalytic activities in the selective oxidation of cyclohexane

Fe, Co, and Mn substituted AlPO-5 molecular sieves, including FeAPO-5, CoAPO-5, MnAPO-5, FeCoAPO-5, FeMnAPO-5, and CoMnAPO-5 were synthesized by hydrothermal method and characterized by X-ray diffraction (XRD), X-ray fluorescence (XRF), scanning electron microscopy (SEM), nitrogen adsorption, and Fourier transform infrared (FT-IR) spectroscopy. The lattice expansions were observed with Fe, Co, and/or Mn substitution of Al atom in AlPO-5. The selective oxidation of cyclohexane to cyclohexanone and cyclohexanol (K/A oil) with molecular oxygen was studied over these catalysts at the reaction temperature of 403 K. The higher activities of the multi-metal substituted AlPO-5, compared to that of single metal substituted AlPO-5, were observed. The underlying reason for the superior activity of the multi-metal substituted AlPO-5 was analyzed.     

Direct and Base Excision Repair-Mediated Regulation of a GC-Rich cis-Element in Response to 5-Formylcytosine and 5-Carboxycytosine

Stepwise oxidation of the epigenetic mark 5-methylcytosine and base excision repair (BER) of the resulting 5-formylcytosine (5-fC) and 5-carboxycytosine (5-caC) may provide a mechanism for reactivation of epigenetically silenced genes; however, the functions of 5-fC and 5-caC at defined gene elements are scarcely explored. We analyzed the expression of reporter constructs containing either 2′-deoxy-(5-fC/5-caC) or their BER-resistant 2′-fluorinated analogs, asymmetrically incorporated into CG-dinucleotide of the GC box cis-element (5′-TGGGCGGAGC) upstream from the RNA polymerase II core promoter. In the absence of BER, 5-caC caused a strong inhibition of the promoter activity, whereas 5-fC had almost no effect, similar to 5-methylcytosine or 5-hydroxymethylcytosine. BER of 5-caC caused a transient but significant promoter reactivation, succeeded by silencing during the following hours. Both responses strictly required thymine DNA glycosylase (TDG); however, the silencing phase additionally demanded a 5′-endonuclease (likely APE1) activity and was also induced by 5-fC or an apurinic/apyrimidinic site. We propose that 5-caC may act as a repressory mark to prevent premature activation of promoters undergoing the final stages of DNA demethylation, when the symmetric CpG methylation has already been lost. Remarkably, the downstream promoter activation or repression responses are regulated by two separate BER steps, where TDG and APE1 act as potential switches.     

光聚合型聚硅氧烷改性聚醚聚氨酯丙烯酸酯低聚物的合成、表征与性能

以羟烷基聚硅氧烷(Q4-3667)、聚丙二醇(PPG-2000)、异佛尔酮二异氰酸酯(IPDI)、二乙醇胺和丙烯酸β-羟乙酯(HEA)为原料合成了一种光聚合型有机硅改性聚醚聚氨酯丙烯酸酯低聚物(Si~5E~5PUA),并用傅里叶红外光谱(FTIR)、核磁共振氢谱(1HNMR)、核磁共振硅谱(29SiNMR)和凝胶渗透色谱(GPC)对其结构进行了表征。详细研究了Si~5E~5PUA与不同单体配比体系的黏度、光聚合性能、聚合过程的体积收缩及其固化膜的玻璃化转变温度。结果表明,Si~5E~5PUA与丙烯酸酯单体具有良好的相容性;其体系具有优异的光聚合性能,最终双键转化率达90%以上,单体官能度的增加可以提高固化膜的玻璃化转变温度,Si~5E~5PUA体系的体积收缩在3.3%~5.6%。     

含5-氨基噻唑环核双酰胺类化合物的合成及生物活性研究

以商品化双酰胺基本骨架为先导,设计并合成了13个含5-氨基噻唑环核的苯甲酰脲类化合物,优化了Thompson等报道的基于Ugi四组件反应2,4二取代-5-氨基噻唑中间体的合成方法,其结构均经1H NMR、13C NMR、IR和MS 分析确证。初步离体杀虫活性测试结果表明,该类化合物具有很好的杀虫活性：当浓度为10 ppm,化合物5f、5g、5h、5j和5m对蚊幼虫均显示100%的杀虫活性,且当浓度降至5 ppm和2 ppm时,化合物5j的活性仍有100%,高于阳性对照;当浓度为600 ppm,化合物5d,5g对棉铃虫和玉米螟均显示100%的杀虫活性。