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1.
通过圆二色谱、稳态吸收光谱、稳态荧光光谱和皮秒时间分辩荧光光谱研究了meso-四(4-(N-甲基吡啶基))卟啉(TMPyP4)与端粒DNA重复序列5'-TTAGGG-3’形成的平行结构DNAG4的相互作用.稳态实验结果表明,二者之间的结合常数为1.29×10^6(mol/L)^-1,饱和结合数为3.将时间分辨荧光光谱应用到二者相互作用的研究中,推测了TMPyP4以插入和末端堆积两种方式与DNAG4相结合.当达到饱和结合时,一个TMPyP4分子插入到DNAG4结构层层之间,另外两个分子以末端堆积的方式结合到G4结构的两端.  相似文献   

2.
在生理酸度pH=7.4条件下,运用荧光光谱、圆二色谱(CD)和傅里叶变换红外光谱(FT-IR)等多种光谱技术,并结合熔点和粘度测量,研究了三氯杀螨醇与小牛胸腺DNA的相互作用模式。实验发现,三氯杀螨醇使DNA的熔点和粘度增大,DNA-溴化乙锭(DNA-EB)复合物的荧光显著猝灭,表明三氯杀螨醇与DNA发生嵌插结合。FT-IR和CD分析推测三氯杀螨醇主要与鸟嘌呤和胞嘧啶碱基结合,并诱导DNA的双螺旋结构和碱基堆积发生一定程度的变化。  相似文献   

3.
基于氧化石墨烯,以修饰了荧光分子的单链DNA为探针,利用荧光光谱和圆二色光谱研究了Ag+对双螺旋DNA中C-C碱基错配特异性识别,并建立了检测Ag+的荧光方法。荧光光谱表明Ag+能与带C-C错配碱基的双螺旋DNA作用,使原本被氧化石墨烯淬灭的标记在DNA上的荧光分子的荧光得到恢复。圆二色光谱表明Ag+能与双螺旋DNA中的C-C碱基错配相互作用,形成更稳定的C-Ag+-C结构。在最佳实验条件下,体系荧光强度的变化与Ag+的浓度在30.0~250.0 nmol/L之间呈良好的线性关系,方法检出限为19.1 nmol/L。为研究Ag+与核酸分子的相互作用及其在环境中对生物分子的影响等方面提供了重要依据。  相似文献   

4.
合成了大黄素类蒽醌衍生物1,4-二甲基-6,8-二甲氧基-9,10-蒽醌(1)并应用紫外光谱、荧光光谱、圆二色谱等方法研究了其与牛血清白蛋白(BSA)和小牛胸腺DNA(ct-DNA)的相互作用.荧光光谱结果表明,化合物1与BSA的相互作用主要以静态猝灭方式使BSA的内源性荧光发生猝灭;圆二色谱表明,化合物1通过疏水作用及形成氢键破坏了α-螺旋结构,导致BSA分子中的α-螺旋含量下降.在pH 7.4时固定DNA的浓度,加入化合物1后,紫外光谱的最大吸收峰发生红移且吸光度加大.荧光光谱表明,化合物1与DNA-4S green NC的结合为竞争性抑制,并可使溶液体系荧光猝灭;圆二色谱表明,随着化合物1的加入,DNA碱基间作用能迅速减弱,表明化合物1与DNA之间为嵌插作用.此外,MTT方法的结果表明,化合物1对结肠癌细胞株HCT116增殖有明显的抑制作用.  相似文献   

5.
在pH7.4Tris-HCl缓冲条件下,应用多种光谱学方法并结合化学计量学多元曲线分辨-交替最小二乘法(MCR-ALS)、DNA熔点测量、粘度分析以及分子模拟技术,研究了环境雌激素双酚A(BPA)与小牛胸腺DNA(ctDNA)的相互作用。由MCR-ALS解析扩展的紫外光谱数据矩阵,得到了3个反应组分(BPA、ctDNA及BPA-ctDNA复合物)的相对浓度及其光谱曲线,可评估BPA与ctDNA相互作用进程。BPA引起ctDNA熔点和粘度升高、与吖啶橙竞争结合ctDNA表明BPA通过嵌插模式与ctDNA作用。傅里叶红外光谱研究显示,BPA主要结合在ctDNA的A,T碱基富集区,这与分子模拟结果一致。圆二光谱分析表明,BPA与ctDNA作用诱导ctDNA的结构由B构象向A构象转变。  相似文献   

6.
2-氨基嘌呤(2Ap)是腺嘌呤的结构类似物, 经常作为荧光探针分子用以研究DNA分子内电荷传递过程. 设计并合成了一系列2-氨基嘌呤和鸟嘌呤核苷酸重复序列GGG之间不同距离的双链DNA分子, 利用时间分辨荧光光谱手段研究了2Ap的荧光衰减动力学以及给体(…GGG…)与受体(2Ap)间的桥体(I, 次黄嘌呤)长度变化对双链DNA电荷传递过程的影响. 结果表明, DNA分子的荧光探针分子2-氨基嘌呤的荧光动力学呈三指数衰减. 其中几百皮秒的组分来源于2-氨基嘌呤和鸟嘌呤之间的电荷转移反应, 当两者间的距离不大于2.4 nm时, 衰减速率随距离的指数函数而减小, 衰减因子b值为1.3 nm−1; 当两者间的距离大于2.4 nm时, 荧光衰减速率随距离增加而加快, 说明电荷转移过程还与桥体次黄嘌呤I的多重复序列能量匹配有关.  相似文献   

7.
一种苊并杂环有机小分子嵌入DNA的几何学模式研究   总被引:2,自引:0,他引:2  
利用圆二色谱(CD)、紫外-可见吸收光谱以及荧光光谱等方法对苊并杂环化合物8-氧-8H-苊并[1,2-b]吡咯-9-腈(A1) 与小牛胸腺DNA(CT DNA) 的相互作用进行了研究. 结果表明, 随着n(A1)/n(CT DNA)的变化存在两种不同的几何学结合构型. 当n(A1)/n(CT DNA)值低于0.20时, A1分子与DNA的结合方式是不均一的, 化合物分子以多种角度嵌入到DNA碱基对之间. 表现为A1-DNA复合物的诱导圆二色光谱图上较小的正峰和紫外吸收光谱图缺省等吸收点. DNA的特征圆二色谱图表明, 在n(A1)/n(CT DNA)≤0.20范围内, CT DNA的构象从标准的B型转化为A-like型; 当n(A1)/n(CT DNA)>0.20时, 诱导圆二色光谱由正峰转变为强度大、波形复杂的负峰, 表明A1分子开始堆积到DNA螺旋的表面, 同时DNA的二级结构发生了进一步变化.  相似文献   

8.
李悦  何华  肖得力  朱鸣阳 《分析测试学报》2015,34(11):1233-1239
采用紫外光谱、荧光光谱结合亚甲基蓝荧光探针(MB)、圆二色谱(CD)以及分子模拟等技术研究了生理条件下杨梅素与小牛胸腺DNA(ct-DNA)的相互作用,探索了其可能的结合位点与作用机制。热力学参数显示ΔH0、ΔS0,说明杨梅素与ct-DNA通过氢键和范德华力发生相互作用。光谱研究显示,ct-DNA能够猝灭杨梅素的内源荧光,猝灭方式为静态猝灭,两者的结合常数为1.86×103mol-1,结合位点数为1。在竞争性实验中杨梅素未能将MB从MB-DNA复合体系中游离出来,说明其与ct-DNA的作用方式为沟槽结合。圆二色光谱研究表明,杨梅素的加入未能破坏ct-DNA的双螺旋结构,两者的作用方式为沟槽结合。进一步通过分子模拟研究得到杨梅素与DNA结合的最低能量构象,杨梅素A环7-O和B环3’-O分别与DNA的碱基DA18和DA6在边缘小沟处通过氢键结合,周围富含碱基A和T,与光谱学研究结果一致,结合距离分别为2.061和1.918。  相似文献   

9.
合成了大黄素类蒽醌衍生物1,4-二甲基-6,8-二甲氧基-9,10-蒽醌(1)并应用紫外光谱、荧光光谱、圆二色谱等方法研究了其与牛血清白蛋白(BSA)和小牛胸腺DNA(ct-DNA)的相互作用。荧光光谱结果表明,化合物1与BSA的相互作用主要以静态猝灭方式使BSA的内源性荧光发生猝灭;圆二色谱表明,化合物1通过疏水作用及形成氢键破坏了α-螺旋结构,导致BSA分子中的α-螺旋含量下降。在p H 7.4时固定DNA的浓度,加入化合物1后,紫外光谱的最大吸收峰发生红移且吸光度加大。荧光光谱表明,化合物1与DNA-4S green NC的结合为竞争性抑制,并可使溶液体系荧光猝灭;圆二色谱表明,随着化合物1的加入,DNA碱基间作用能迅速减弱,表明化合物1与DNA之间为嵌插作用。此外,MTT方法的结果表明,化合物1对结肠癌细胞株HCT116增殖有明显的抑制作用。  相似文献   

10.
为考察小分子配基与不同核酸结构的结合机理,发展新的核酸探针分子,合成了一种新型一次甲基不对称菁染料(MTP).吸收光谱、荧光光谱及圆二色光谱研究结果表明,MTP可与平行和混合平行G-四链体DNA(如c-myc和22AGK+)较强地结合,并引起130~180倍的荧光增强;其与单/双链DNA作用较弱,导致40~60倍荧光增强;而与反平行G-四链体DNA(如TBA和22AGNa+)的作用最弱,只引起15~25倍荧光增强;以上结果表明MTP可作为荧光探针分子用于区别不同结构的核酸分子.结合机理研究表明,平行和混合平行G-四链体DNA优先通过沟槽结合模式结合1分子MTP,再通过末端堆积模式结合另1分子MTP.  相似文献   

11.
The spectral properties of meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) bound to poly(dA).poly(dT) and poly[d(A-T)(2)] in the presence and in the absence of 4',6-diamidino-2-phenylindole (DAPI) have been studied. DAPI fits deeply into the minor groove of both poly(dA).poly(dT) and poly[d(A-T)(2)], and TMPyP is also situated at the minor groove. The nature of the absorption, circular dichroism (CD), and flow linear dichroism (LD) spectra of the TMPyP-poly(dA).poly(dT) and -poly[d(A-T)(2)] complexes in the Soret band is essentially unaffected whether the minor groove is blocked by DAPI or not, although small variations been noticed in the presence of DAPI. Furthermore, a close analysis of the reduced LD spectrum in the Soret band results in angles of approximately 80 degrees and 55 degrees between transition moments of the TMPyP and DNA helix axes in the absence of DAPI. All these observations indicate that the side of TMPyP whose structure resembles that of classical minor groove binding drugs does not fit deeply into the minor groove. This suggests that TMPyP binds across the minor groove: two positively charged pyridiniumyl rings interact electrostatically with negatively charged phosphate groups of DNA. When DAPI and TMPyP are simultaneously bound to poly(dA).poly(dT) or poly[d(A-T)(2)], the fluorescence intensity of DAPI decreases as TMPyP concentration increases, indicating that the excited energy of DAPI is transferred to TMPyP.  相似文献   

12.
Abstract— The hydrophobic interactions of bulky polycyclic aromatic hydrocarbons with nucleic acid bases and the formation of noncovalent complexes with DNA are important in the expressions of the mutagenic and carcinogenic potentials of this class of compounds. The fluorescence of the polycyclic aromatic residues can be employed as a probe of these interactions. In this work, the interactions of the (+)-trans stereoisomer of the tetraol 7,8,9,10-tetrahydroxytetrahydrobenzo[a]pyrene (BPT), a hydrolysis product of a highly mutagenic and carcinogenic diol epoxide derivative of benzo[a]pyrene, were studied with 2′-deoxynucleosides in aqueous solution by fluorescence and UV spectroscopic techniques. Ground-state complexes between BPT and the purine derivatives 2′-deoxyguanosine (dG), 2′-deoxyadenosine (dA), and 2′-deoxyinosine (dI) are formed with association constants in the range of ~40–130 M?1 Complex formation with the pyrimidine derivatives 2′-deoxythymidine (dT), 2′-deoxycytidine (dC), and 2′-deoxyuridine (dU) is significantly weaker. Whereas dG is a strong quencher of the fluorescence of BPT by both static and dynamic mechanisms (dynamic quenching rate constant kdyn= [2.5 ± 0.41 × 109M1 s 1, which is close to the estimated diffusion-controlled value of ~ 5 × 109M? 1 s?1), both dA and dI are weak quenchers and form fluorescenceemitting complexes with BPT. The pyrimidine derivatives dC, dU, and dT are efficient dynamic fluorescence quenchers (Kdyn~ [1.5–3.0] × 109M?1 s?1), with a small static quenching component due to complex formation evident only in the case of dT. None of the four nucleosidcs dG, dA, dC and dT are dynamic quenchers of BPT in the triplet excited state; the observed lower yields of triplets are attributed to the quenching of single excited states of BPT by 2′-deoxynucleosides without passing through the triplet manifold of BPT. Possible fluorescence quenching mechanisms involving photoinduced electron transfer are discussed. The strong quenching of the fluorescence of BPT by dG, dC and dT accounts for the low fluorescence yields of BPT-native DNA and of pyrene-DNA complexes.  相似文献   

13.
Triplex-forming oligonucleotides (TFOs) containing 9-deazaguanine N7-(2′-deoxyribonucleoside) 1a and halogenated derivatives 1b,c were synthesized employing solid-phase oligonucleotide synthesis. For that purpose, the phosphoramidite building blocks 5a – c and 8a – c were synthesized. Multiple incorporations of 1a – c in place of dC were performed within TFOs, which involved the sequence of five consecutive 1a – c ⋅ dG ⋅ dC triplets as well as of three alternating 1a – c ⋅ dG ⋅ dC and dT ⋅ dA ⋅ dT triplets. These TFOs were designed to bind in a parallel orientation to the target duplex. Triplex forming properties of these oligonucleotides containing 1a – c in the presence of Na+ and Mg2+ were studied by UV/melting-curve analysis and confirmed by circular-dichroism (CD) spectroscopy. The oligonucleotides containing 1a in the place of dC formed stable triplexes at physiological pH in the case of sequence of five consecutive 1a ⋅ dG ⋅ dC triplets as well as three alternating 1a – c ⋅ dG ⋅ dC and dT ⋅ dA ⋅ dT triplets. The replacement of 1a by 9-halogenated derivatives 1b,c further enhanced the stability of DNA triplexes. Nucleosides 1a – c also stabilized duplex DNA.  相似文献   

14.
We investigated the molecular recognition between the amphiphile AzoAde, which is composed of azobenzene in the hydrophobic and adenine in the hydrophilic portion of the molecule, and oligonucleotides having a homogeneous base (dA30, dT30, dG30, and dC30) at the air-water interface. On the basis of the complementary base-pairing of DNA in the duplex, orderly arrangement of AzoAde on templated dT30 was examined using pi-A isotherm, UV-vis RAS, FT-IR RAS, and XPS measurements. Although there was little interaction between AzoAde and mismatched oligonucleotides (dA30, dG30, and dC30), AzoAde prepared on a dT30 subphase stoichiometrically assembled and interacted with dT30, subsequently forming a J-form assembly at the air-water interface. AFM observation of the LB films revealed the nanostructure of the J-formed AzoAde monolayer on the dT30 subphase as well as the domain structures of the H-formed monolayers on the other oligonucleotide subphases. Therefore, dT30 has a potential application as a template for assembling AzoAde at the air-water interface.  相似文献   

15.
The deoxyribonucleosides have been studied to determine the properties of combinations of 2-deoxyribose with each of the isolated DNA bases for both neutral and anionic species. We have used a carefully calibrated theoretical method [Chem. Rev. 2002, 102, 231], employing the B3LYP hybrid Hartree-Fock/DFT functional with the DZP++ basis set. Predictions are made of the geometric parameters, adiabatic electron affinities, charge distributions based on natural population analysis, and decomposition enthalpy for the neutral and anionic forms of the four 2'-deoxyribonucleosides in DNA: 2'-deoxyriboadenosine (dA), 2'-deoxyribocytidine (dC), 2'-deoxyriboguanosine (dG), and 2'-deoxyribothymidine (dT). Geometric changes in the anions show that the glycosidic bond exhibits little change with excess charge for the guanosine but significant shortening for the adenosine and for the pyrimidines. The zero-point corrected adiabatic electron affinities in eV for each of the 2'-deoxyribonucleosides are as follows: 0.06, dA; 0.09, dG; 0.33, dC; and 0.44, dT. These values are uniformly greater than those of the corresponding isolated bases (-0.28, A; -0.07, G; 0.03, C; 0.20, T) and the isolated 2-deoxyribose (-0.38) at the same level of theory. The vertical detachment energies of dT and dC are substantial, 0.72 and 0.94 eV, and these anions should be observable. A high VDE, 0.91 eV, is also found for dA but its anion is unlikely to be stable due to the small AEA of 0.06 eV. The high VDE reflects the fact that the molecular structures of the anions and the corresponding neutral species are quite different. Valence character is displayed for the SOMOs of dA, dC, and dT, while some component of diffuse character is visible in the SOMO of dG. Further analysis of electronic changes upon electron attachment include an examination of the NPA charges, which show that in the neutral 2'-deoxyribonucleosides the sum of NPA charges for every base is the same, -0.28 with the sum of 2-deoxyribose charges being positive, +0.28. In the anions, the trend in charge division varies based on the nature of the excess electron in the anions. Thermodynamically, the overall enthalpy change for the reaction of water with the neutral nucleosides to give bases and ribose is approximately zero. The analogous decomposition is exothermic by 8 to 11 kcal mol-1 for the anions, indicating possible challenges for anionic gas-phase nucleoside exploration in the presence of water.  相似文献   

16.
We synthesized two water-soluble porphyrins appending platinum(II) complexes [alpha,beta-(4a) and alpha,alpha-(4b) 5,15-bis(2-trans-[PtCl(NH3)2]N-2-aminoethylaminocarbonylphenyl) 2,3,7,8,12,13,17,18-octamethylporphyrin] and studied their reactions with a variety of nucleic acids [disodium adenosine-5'-monophosphate (AMP), disodium guanosine-5'-monophosphate (GMP), disodium thymidine-5'-monophosphate (TMP), disodium cytidine-5'-monophosphate (CMP), synthetic polymer poly(dG)-poly(dC), poly(dA)-poly(dT)] by 1H-NMR, UV-vis and FAB-MS spectroscopies. Based on the denaturation experiments of synthetic nucleic acid polymers, we conclude that the presence of the porphyrins (5.6 microM) does not cause significant changes in the melting temperature of poly(dA)-poly(dT) (28 microM) (deltaT=1 degrees C) and shows reannealing. On the other hand, gradual melting of poly(dG)-poly(dC) (28 microM) occurs at a low temperature (deltaT= -27 degrees C) in the presence of the porphyrins (5.6 microM), and the solutions do not show reannealing phenomena. The results of UV-vis and 1H-NMR experiments revealed that the porphyrins bind to guanine bases and that the porphyrins bind to GMP more strongly than to the other nucleotides. The binding modes between the porphyrins and synthetic nucleic acids are affected more by the coordination of the nucleobase [poly(dG)-poly(dC)] to the Pt(II) in the porphyrins than by Coulomb and hydrophobic interactions.  相似文献   

17.
18.
For the first time ssDNA (25‐aptamer of mixed dA, dT, dG, and dC) was wrapped around functionalized single‐walled carbon nanotubes (SWCNTs), whose external surfaces were attached to multiple triazole‐(ethylene glycol)‐dA ligands. This method of hybridization involved the formation of hydrogen bonds between dT of ssDNA and dA of functionalized SWCNTs. It deviates from the reported π–π stacking between the nucleobases of DNA and the external sidewalls of nanotubes. The structural properties of the functionalized SWCNTs and its ssDNA complex were characterized by spectroscopic (including CD and Raman), thermogravimetric, and microscopic (TEM) methods. The results thus obtained establish a new platform of DNA delivery by use of nanotubes as a new vehicle with great potential in biomedical applications and drug development.  相似文献   

19.
This work describes the in situ synthesis of oligonucleotide arrays on glass surfaces. These arrays are composed of features defined and separated by differential surface tension (surface tension arrays). Specifically, photolithographic methods were used to create a series of spatially addressable, circular features containing an amino-terminated organosilane coupled to the glass through a siloxane linkage. Each feature is bounded by a perfluorosilanated surface. The differences in surface energies between the features and surrounding zones allow for chemical reactions to be readily localized within a defined site. The aminosilanation process was analyzed using contact angle, X-ray photoelectron spectroscopy (XPS), and time-of-flight/secondary ion mass spectroscopy (TOF-SIMS). The efficiency of phosphoramidite-based oligonucleotide synthesis on these surface tension arrays was measured by two methods. One method, termed step-yields-by-hybridization, indicates an average synthesis efficiency for all four (A,G,C,T) bases of 99.9 +/- 1.1%. Step yields measured for the individual amidite bases showed efficiencies of 98.8% (dT), 98.0% (dA), 97.0% (dC), and 97.6% (dG). The second method for determining the amidite coupling efficiencies was by capillary electrophoresis (CE) analysis. Homopolymers of dT (40- and 60mer), dA (40mer), and dC (40mer) were synthesized on an NH(4)OH labile linkage. After cleavage, the products were analyzed by CE. Synthesis efficiencies were calculated by comparison of the full-length product peak with the failure peaks. The calculated coupling efficiencies were 98.8% (dT), 96.8% (dA), and 96.7% (dC).  相似文献   

20.
Oligonucleotides incorporating the unusually linked 8-aza-7-deazapurine N8-(2'-deoxyribonucleosides) 3a,b (purine and 6-amino-2-chloropurine analogues) were used as chemical probes to investigate the base pairing motifs of the universal nucleoside 8-aza-7-deazapurin-6-amine N8-(2'-deoxyribofuranoside) 2 (adenine analogue) and that of the 2,6-diamino compound 1. Owing to the absence of an amino group on the nucleoside 3a the low stability of oligonucleotide duplexes incorporating this compound opposite to the four canonical DNA-constituents indicate hydrogen bonding and base pairing for the universal nucleosides 1 and 2 which form much more stable duplexes. When the 6-amino-2-chloro-8-aza-7-deazapurine nucleoside 3b replaces 1 and is located at the same positions, two sets of duplexes are formed (i) high Tm duplexes with 3b located opposite to dA or dC and (ii) low Tm duplexes with 3b located opposite to dG or dT. These results are due to the steric clash of the 2-chloro substituent of 3b with the 2-oxo group of dT or the 6-oxo group of dG while the 2-halogeno substituents are well accommodated in the base pairs formed with dA or dC. For comparison duplexes incorporating the regularly linked nucleosides 4-6a,b containing the same nucleobases as those of 1-3a,b were studied.  相似文献   

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