富勒烯半胱氨酸的固相合成与荧光特性

基于氨基与富勒烯之间的加成反应与多肽的固相有机合成,合成了一种单加成富勒烯半胱氨酸(fullerene cystine,Fcy).采用有机溶剂交换法制备了Fcy的纳米颗粒水悬液n-Fcy,并比较了Fcy与n-Fcy的荧光性质.     

Experimental Designs Applied to Solid-Phase Derivative Spectrophotometry

 Using two statistical models, based on the two-level full factorial designs and sequential experimental Doehlert designs, a simultaneous determination of cadmium and zinc by solid-phase derivative spectrophotometry has been proposed. These chemometric techniques have been used for the optimization of the instrumental and experimental variables of the system. The complexes formed between cadmium and zinc with 4-(2-pyridylazo) resorcinol, in the presence of potassium iodide, were fixed on a dextran-type anion-exchange gel, at pH 8.7. The absorbance spectra of the gel, packed in a 1-mm cell, were recorded directly. The performance characteristics of the proposed method have been established. The method was applied to the simultaneous determination of both analytes in synthetic mixtures and natural water samples. Received November 26, 1998. Revision November 10, 1999     

Development of Electro Solid-Phase Microextraction and Application to Methamphetamine Analysis

A new electro solid-phase microextraction (El-SPME) technique using homemade pencil-lead fibers has been developed as an effective means of selective extraction of methamphetamine before analysis by gas chromatography (GC) and gas chromatography–mass spectrometry (GC–MS). The methamphetamine was extracted by use of a laboratory-made El-SPME cell with three electrodes—the pencil-lead SPME fiber, Ag/AgCl, and platinum as working, reference, and auxiliary electrodes, respectively. A negative potential was applied to the homemade pencil-lead fiber during extraction. Experimental conditions, for example type of pencil-lead fiber, conditions for modification of the fiber, extraction time, applied potential, pH, and gas chromatographic conditions were optimized. Methamphetamine was identified by GC–MS. Screening of the extracted compounds showed that the proposed El-SPME technique is much more selective than direct SPME using a commercially available polyacrylate fiber. Under the optimum conditions the calibration plot for the compound was linear in the range 50–3,200 ng mL⁻¹ and the detection limit was 34 ng mL⁻¹.     

有机硅连接体在固相有机合成中的应用

固相合成方法具有传统液相反应无可比拟的优越性,已被越来越多的化学家认可.反应物与高分子支持体的连接则是固相合成中的重要环节,连接体在其中扮演着重要的角色.近20多年来发展起来的有机硅连接体基本满足了理想连接体的要求,具有广阔的应用发展前景.本文从直接法和间接法两方面综述了26年来具有代表性的多种有机硅连接体的设计、制备及其在固相有机合成中的应用.     

2,9-双甲基苯并噻唑乙烯基邻菲罗琳与DNA 的相互作用及应用研究

设计合成了基于2,9-双苯并噻唑乙烯基取代的邻菲罗琳荧光分子—PMBT。通过吸收光谱、荧光光谱、圆二色光谱探讨了PMBT与不同DNA的相互作用。发现PMBT与DNA存在两种不同的相互作用模式。 由于PMBT分子中带有两个正电荷,当PMBT与DNA的浓度比值较高（大于4）时,PMBT以DNA为模板按一定方向在DNA上聚集;当PMBT与DNA的浓度比小于2时,PMBT通过嵌插或末端堆积的方式分别与单/双链DNA和G-四链体DNA结合。PMBT与DNA结合导致其荧光淬灭,利用该特性将PMBT与DNA结合构建荧光增强型检测平台,可用于DNA酶活性以及DNA降解的动力学研究。     

一种新型三肽衍生物改性聚氨酯的合成和应用

合成了一种新型三肽衍生物苯丙氨酸-赖氨酸乙酯-苯丙氨酸（PLP）。以PLP为扩链剂、聚己内酯二醇（PCL）为软段、4,4′-二环己基甲烷二异氰酸酯（HMDI）为硬段,合成了一系列不同三肽含量的聚氨酯（PU-PLP）。通过1H-NMR、FT-IR、TG、DSC和黏接强度等对PLP和PU-PLP的结构和性能进行了研究。结果...     

Solid-Phase Synthesis of Macrocyclic Systems by a Cyclorelease Strategy: Application of the Stille Coupling to a Synthesis of (S)-Zearalenone

No heteroatom required! In many solid-phase syntheses, after the release from the polymer support a heteroatom (e.g. O, S, N) remains in the substrate as a residue of a linking protecting group. With polymer-bound tin reagents cleavage and cyclization of the substrate with C–C bond formation (see picture) can now be achieved by intramolecular Stille coupling. S =substrate.     

Solid-Phase Synthesis of Thio-oligosaccharides

No protecting groups are present in the highly reactive polymer-bound sugar 1-thiolates 1 , which undergo reactions with sugar triflates 2 to give thio-oligosaccharides 3 in high yield. Tr=trityl=triphenylmethyl, Tf=trifluoromethylsulfonyl, Bz=benzoyl.     

胡蜂蜂毒肽的固相合成

采用Fmoc固相合成策略,合成了胡蜂蜂毒肽(COOH-Ile-Asn-Leu-Lys-Ala-Leu-Ala-Ala-Leu-Ala-Lys-Lys-Ile-Leu-NH₂)。以Wang树脂为载体,HBTU-HOBt为缩合剂,按照其氨基酸序列依次缩合,最终用切割试剂将其从树脂上切割下来,得到粗肽,经RP-HPLC纯化得到目标肽,纯度97.6%。经HR-MS（EI）分析,确定产物为胡蜂蜂毒肽。     

黄酮类衍生物的合成

按照药物拼合原理,在黄酮分子中引入具有降血脂作用的丹皮酚(5,中药丹皮的有效成分)和非诺贝特的结构特征:对羟基苯甲醛(2)与氯乙酸乙酯通过Williamson反应制得对醛基苯氧基乙酸乙酯(3);3水解得对醛基苯氧基乙酸(4);4与5经羟醛缩合制得(E)-2-14-[3-(2·羟基4-甲氧基苯基)-3-氧代丙烯-1-基]...     

Development of Rapid and Facile Solid-Phase Synthesis of PROTACs via a Variety of Binding Styles

Optimizing linker design is important for ensuring efficient degradation activity of proteolysis-targeting chimeras (PROTACs). Therefore, developing a straightforward synthetic approach that combines the protein-of-interest ligand (POI ligand) and the ligand for E3 ubiquitin ligase (E3 ligand) in various binding styles through a linker is essential for rapid PROTAC syntheses. Herein, a solid-phase approach for convenient PROTAC synthesis is presented. We designed azide intermediates with different linker lengths to which the E3 ligand, pomalidomide, is attached and performed facile PROTACs synthesis by forming triazole, amide, and urea bonds from the intermediates.     

Development of Palladium-catalyzed Cycloalkenylation and its Application to Bioactive Natural Product Synthesis

Stereoselective total syntheses of (±)-aphidicolin and (–)-serofendic acids A and B have been achieved by means of palladium-catalyzedcycloalkenylation.     

Evaluation of Binding Between Electroactive Biotin Derivative and Streptavidin Immobilized on Chitin Film

Evaluation of the streptavidin‐biotin binding at the surface of chitin film was carried out with voltammetry. Immobilization of streptavidin was attempted to the protonated chitin film, based on an electrostatic interaction that hardly causes any change in the protein structure. The streptavidin‐biotin binding was estimated from changes in the electrode response of biotin labeled with an electroactive compound. Although the response of daunomycin as an electroactive compound did not change at an electrode covered with streptavidin/chitin film, the response of the labeled biotin decreased. This observation shows that streptavidin is immobilized on the chitin film and the biotin binds with immobilized streptavidin. Consequently, it was clear that the chitin film is useful as a reaction field for protein‐ligand binding. Generally, a binding event between protein and its ligand in the living body occurs on the cell surface. The electrochemical evaluation of protein‐ligand binding on a natural polysaccharide like chitin membrane surface is important.     

A Tripeptide Approach to the Solid-Phase Synthesis of Peptide Thioacids and N-Glycopeptides

A general and robust method for the incorporation of aspartates with a thioacid side chain into peptides has been developed. Pseudoproline tripeptides served as building blocks for the efficient fluorenylmethyloxycarbonyl (Fmoc) solid-phase synthesis of thioacid-containing peptides. These peptides were readily converted to complex N-glycopeptides by using a fast and chemoselective one-pot deprotection/ligation procedure. Furthermore, a novel side reaction that can lead to site-selective peptide cleavage using thioacids (CUT) was discovered and studied in detail.     

新型沙美特罗衍生物的合成

以沙美特罗的缩酮保护产物为原料,经长链仲氨的叔丁氧羰基保护、分子内酯交换反应选择性保护氨基间位的苄羟基、脱缩酮保护、与昔萘酸甲酯的Friedel-Crafts反应后再经碱水解合成了一个新型的沙美特罗衍生物——1-羟基-4-【2-羟基-5-【1-羟基-2-{[6-(4-苯丁氧基)]己氨基}乙基】苯甲基】-2-萘甲酸,总收率16.3%,其结构经1H NMR和MS表征。     

一种新的四硫富瓦烯衍生物的合成

经偶联、缩合等反应合成了一种新的用于分子组装的底物2,3-(二硫甲基)-6,7(二硫丁氧基对苯亚甲基巴比妥)四硫富瓦烯,产物用元素分析,IR和^1H NMR进行了表征,并初步探讨了其电化学行为。     

新型萘酰亚胺衍生物的合成

N-(N’,N’-二甲基氨基乙基)-4-硝基-1,8-萘酰亚胺和2,3-二甲基苯并噻唑碘化盐在痕量水存在下经亲核取代反应合成了一个新型的萘酰亚胺衍生物——N-(N’,N’-二甲基氨基乙基)-4-[2-(2,3-二氢-2,3-二甲基苯并噻唑)氧基]-1,8-萘酰亚胺,其结构经1H NMR,13C NMR和ESI-MS表征。并对反应机理进行了初步研究。     

苯甲酰苯并咪唑衍生物的合成

以3,5-二甲基-1H-吡咯-2-甲酸乙酯(2)为起始原料,与新型Vilsmeier试剂反应得4-甲酰基-3,5-二甲基-1H-吡咯-2-甲酸乙酯(3);3与3,4-二氨基二苯甲酮环合制得4-(5-苯甲酰-1H-苯并咪唑-2-基)-3,5-二甲基-1H-吡咯-2-甲酸乙酯(4);4水解后与2-吡唑啉经脱水反应合成了一个苯并咪唑衍生物,总收率54%,其结构经1H NMR,13C NMR和MS确证。