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1.
基于晶体场理论,本文采用重叠模型和3d9电子组态在畸变四角晶场中的g因子和超精细结构常数A的三阶微扰计算公式以及钛酸铅PbTiO3 (PTO): Cu2+晶体的局域结构与EPR谱之间的定量关系,合理解释了PTO: Cu2+晶体的EPR谱及局域晶体结构,所得结果与实验观测相符合.   相似文献   

2.
G群链球菌G蛋白的B1结构域——GB1蛋白,常被用作发展体外及体内基于顺磁核磁共振(NMR)的蛋白质结构测定方法的研究模型.为确保赝接触化学位移(PCS)、顺磁弛豫增强(PRE)等顺磁约束数据的准确性,了解GB1和金属离子,尤其是顺磁离子的相互作用非常必要.然而GB1和二价金属离子以及镧系金属离子的相互作用并不十分清楚.本文利用NMR波谱研究了GB1和镧系金属离子以及多种二价金属离子的相互作用.我们发现GB1和镧系金属离子之间存在弱特异性相互作用,和Mn2+、Cu2+以及Co2+等顺磁二价离子弱结合,但不与Ca2+、Mg2+以及Zn2+等抗磁二价离子结合.该研究表明在GB1上链接顺磁探针时,应使用与固有位点结合常数差异明显的顺磁标签以获取正确的PRE数据.  相似文献   

3.
通过L-谷氨酸苄酯和三光气反应制备谷氨酸苄酯的N-羧酸酐,以聚羟乙谷氨酸酰胺为大分子引发剂,投入不同配比的单体/引发剂(A/I),共聚得到两亲性嵌段共聚物聚羟乙谷氨酰胺-聚谷氨酸苄酯(PHEG-PBLG);通过核磁共振技术分析表征该合成聚肽的结构组成、分子量范围及螺旋结构;通过体外酶解实验研究了共聚物的降解情况. 研究结果表明:该合成聚肽化合物为两亲性嵌段聚合物:当聚合物中亲水链段PHEG分子量为9000,A/I为75∶1, 100∶1, 150∶1, 200∶1时,相应的共聚物的分子量分别为:1.27×104,1.75×104, 1.9×104, 3.60×104;该合成聚肽含有α-螺旋结构, 随着TFA的加入,该聚肽的结构由α-旋构象转化为随机盘绕构象.  相似文献   

4.
PhoB是PhoR/PhoB双组分信号转导系统(TCS)中的应答调控蛋白,来自大肠杆菌,可以参与环境中自由Pi的调控应答.PhoB拥有保守的磷酸化位点D53,当Mg2+存在时,会变成活性构象,但是其中的机理尚不清楚.目前已经有报道指出,自由态的应答调控蛋白存在少量的活性构象,而且它们和蛋白的激活过程相关,但是这种活性构象一般不稳定,很难观测到.本文以PhoBNF20D作为模型,1H-15N HSQC和19F NMR谱图显示,自由态PhoBNF20D在溶液中存在pre-active构象,BeF3-可以稳定这种活性构象,而且Mg2+可以促进非活性构象到活性构象之间的转化,在BeF3-存在的情况下可以使PhoBNF20D形成完全的活性构象.同时我们利用Carr-Purcell-Meiboom-Gill(CPMG)弛豫弥散实验证明了PhoBNF20D存在两态交换.  相似文献   

5.
应用圆二色谱、内源荧光和外源荧光探针研究了丝素蛋白在甲醇-水混合溶剂中的构象变化及机理。结果显示,在浓度低于30%(V/V)的甲醇-水混合溶剂中,处于无规卷曲状态的丝素蛋白可以通过疏水相互作用形成小的疏水区域,随着甲醇浓度的增加,丝素蛋白发生由无规卷曲向β-折叠的构象转变,削弱了疏水侧链的相互作用。分析表明,丝素蛋白的构象变化与溶剂体系的微观结构密切相关,其稳定性主要由肽键单元与混合溶剂中的分子簇之间的相互作用决定。低浓度的甲醇-水混合溶剂保持水固有的氢键结构,对丝素蛋白肽键单元的溶剂化和丝素蛋白构象的影响较小,而随着甲醇浓度的增加,溶剂结构出现由四面体结构的水分子簇向链状结构的甲醇分子簇的转变,丝素蛋白通过形成分子内氢键减少肽键单元与溶剂分子的接触,从而引发丝素蛋白的构象转变。  相似文献   

6.
丁酸氯维地平的波谱学数据与结构确证   总被引:2,自引:1,他引:1  
丁酸氯维地平是一种短效二氢吡啶类钙通道阻滞剂,对丁酸氯维地平的紫外吸收光谱(UV)、红外吸收光谱(IR)、核磁共振氢谱(1H NMR)、氢-氢相关谱(1H-1H COSY)、核磁共振碳谱13C NMR、DEPT谱、碳氢相关谱(HMQC)、碳氢远程相关谱(HMBC)及质谱(MS)进行了解析,对其所有的NMR谱信号进行了归属;讨论了红外光谱特征吸收峰所对应的官能团的振动形式,确证了丁酸氯维地平的结构.  相似文献   

7.
近年来,萤火虫荧光素酶催化的生物发光反应被广泛的应用到ATP检测、细菌数目检测、环境监测和其他生物学研究之中。通过对中华黄萤荧光素酶的性质研究,发现其分子量为6 400左右,是一种非典型的Michaelis-Menten氏酶,对底物之一的ATP动力学曲线为S型。最适反应温度为20~25℃,对温度极其敏感,当反应温度高于30℃时,该酶的活性快速失活。该荧光素酶的最适pH=6.5。随着pH值的下降该荧光素酶生物发光的最大发射光波长没有明显的红移现象。Mg2+和Mn2+对该酶活性的激活效果比较接近,最佳的激活浓度均在1mmol/L附近,而Ca2+最佳的激活浓度则小于1 mmol/L,且激活的效果只有Mg2+作用效果的50%左右。和Hg2+、Cd2+等离子一样,Cu2+会在一定程度上抑制该荧光素酶的活性。该酶的稳定性较差,对盐浓度和光照比较敏感,高浓度的盐类和长时间的日光照射能够使酶失活。谷胱甘肽(GSH)和二硫苏糖醇(DTT)是该酶较好的保护剂,可以提高该酶在一定时间内的稳定性,其中前者的作用效果要好于后者。  相似文献   

8.
300 MHz核磁共振频率源的研制   总被引:1,自引:1,他引:0  
乔勇  季文彬  蒋瑜 《波谱学杂志》2006,23(4):494-501
介绍了基于Analog Device公司AD9954设计的数字化频率源,可以实现宽带高频(5 MHz~125 MHz、280 MHz~301 MHz)、高稳定度(1×10-9)、低相位噪声(301 MHz,≤-127 dBc/Hz@250 kHz offset)频率输出以及频率、相位和幅度的高速切换. 该数字化频率源可应用于300 MHz核磁共振谱仪和磁共振成像仪,可部分取代昂贵的进口频率源. 本文最后给出核磁实验结果.  相似文献   

9.
2D NMR技术在多季碳二萜结构确定中的应用   总被引:1,自引:1,他引:0  
应用二维核磁共振技术(2D NMR:1H-1H COSY、HMQC、HMBC), 尤其是HMBC谱准确归属了多季碳二萜伊丽莎白素B(Elisabatin B)的1H,13C信号,并经与已报道的数据比较,进一步明确指定了11个季碳的化学位移. 以伊丽莎白素B为例,较系统阐明了几种二 维核磁共振技术在天然产物结构确定中的作用和方法.  相似文献   

10.
刘静  谈光华  张帆  马静  王静静 《发光学报》2018,39(4):573-579
以1,8-萘酰亚胺、壳聚糖、盐酸吗啉胍为原料,通过酰亚胺化、席夫碱等反应,设计合成了一种萘酰亚胺接枝壳聚糖类增强型荧光探针(NCFP)。采用红外、核磁共振等技术对其结构进行表征,利用荧光光谱研究了其光谱性能及对金属离子的识别作用。研究结果表明,合成的荧光探针对Al3+具有较高的选择识别性能,且受常见离子的干扰较小。探针的荧光强度与Al3+浓度(29.90~253.41 μmol/L)有良好的线性关系,线性相关系数R2=0.997 9,Al3+的最低检出限达4.279 μmol/L,Job's曲线表明,荧光探针与Al3+的络合比为1:1。  相似文献   

11.
12.
为什么蚕在常温常压水溶液条件下即能纺出力学性能优异的蚕丝纤维,一直是科学家们感兴趣的问题. 在过去的几十年,人们曾用多种表征手段,如双折射、扫描电镜、原子力显微镜和电子散射等,在界观尺度下对蚕在吐丝过程中腺体的相行为进行研究. 发现腺体在靠近吐丝口时呈液晶态,并认为这是导致蚕丝力学性能的重要因素. 本文则在分子水平尺度下利用核磁共振方法, 对五龄蚕活体在常温和6 ℃下存储数天后解剖的腺体进行研究. 经对化学位移及其线型的各向异性分析发现,当将体内腺体沿吐丝方向分为3部,即后部、中部及靠近吐丝口的前部时,常温下,腺体后部和中后部分子呈无规线团,而腺体中中部、中前部和前部分子呈液晶态. 6 ℃时, 中后部分子亦呈液晶态,前部分子排列则各向异性更大,说明更为有序. 这种液晶态呈分形结构,在小于纳米尺度下为无规线团,大于纳米尺度呈有序排列. 这表明,降温过程可使呈无规线团的丝素蛋白分子转变为液晶态,其效果如同蚕在吐丝过程中对其腺体施加的剪切应力. 该结果对于人们探索人工合成高性能类丝素纤维的纺丝工艺和条件将有启发和指导作用.   相似文献   

13.
The local structure of titanium pair centers in SrF2: Ti crystals is investigated using electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy. It is found that titanium pair centers with spin moment S=2 and tetragonal symmetry of the magnetic properties are formed in SrF2: Ti cubic crystals under certain growth conditions and during annealing. The tensor components of the fine and ligand hyperfine structures in the EPR and ENDOR spectra are determined. A model of the Ti+-Ti3+ paramagnetic dimer is proposed. This model provides an adequate interpretation of both the ferromagnetic nature of the exchange interaction and the observed displacements of four ligands in the first coordination sphere of titanium impurity ions in directions perpendicular to the impurity ion-ligand bonds.  相似文献   

14.
The interaction between Mn and Cu ions is studied by measuring the resistance and electron paramagnetic resonance (EPR) at different temperatures of the Cu-doped compound La2/3Ca1/3Mn1−xCuxOy. A new transition inR-T curve and substantial enhancement in magnetoresistance are induced by the substitution of Mn ions by Cu ions. The EPR measurement shows that two resonance signals appear at temperature lower than the spin-ordering temperature of Mn ions. A tentative interpretation for the observed phenomena is proposed by considering the interaction between the Cu/Mn ions besides the Mn3+/Mn4+ ions.  相似文献   

15.
As a continuation of our previous study of Cu(II) ternary complexes, two new systems containing 5-chlorosalicylic acid (5-ClsalH) and different Cu(II) salts, with varying N,N-diethylnicotinamide (denia) concentrations, system III [CuSO4(aq) + 2(5-ClsalH(solv)) + xdenia(l)] and system IV [Cu(ac)2(aq) + 2(5-ClsalH(solv)) + xdenia(l)], where x = 0, 2, 4, 6 and 8, were prepared. The effects of Cu(II) salts containing anions of different basicity and N-donor ligand (denia) with varying ligand-to-metal ratio (x) on the formation of resulting complexes were studied by electron paramagnetic resonance (EPR) spectroscopy in frozen water–methanol solutions. Well-resolved 14N superhyperfine splitting lines (nonet) in the perpendicular region of the second-derivative axially symmetric Cu(II) EPR spectra indicated that for x > 4 in system III and for x ≥ 2 in system IV, four equivalent nitrogens could be coordinated to the central Cu(II) ions in the equatorial plane. Such information cannot be obtained by EPR spectroscopy of powder samples of the given Cu(II) complex systems. The differences between denia and ronicol containing Cu(II) complexes are discussed.  相似文献   

16.
When Silk fibre derived from Bombyx mori, a native biopolymer, was dissolved in highly concentrated neutral salts such as CaCl2, the regenerated liquid silk, a gradually degraded peptide mixture of silk fibroin, could be obtained. The silk fibroin nanoparticles were prepared rapidly from the liquid silk by using water-miscible protonic and polar aprotonic organic solvents. The nanoparticles are insoluble but well dispersed and stable in aqueous solution and are globular particles with a range of 35–125 nm in diameter by means of TEM, SEM, AFM and laser sizer. Over one half of the ɛ-amino groups exist around the protein nanoparticles by using a trinitrobenzenesulfonic acid (TNBS) method. Raman spectra shows the tyrosine residues on the surface of the globules are more exposed than those on native silk fibers. The crystalline polymorph and conformation transition of the silk nanoparticles from random-coil and α-helix form (Silk I) into anti-parallel β-sheet form (Silk II) are investigated in detail by using infrared, fluorescence and Raman spectroscopy, DSC, 13C CP-MAS NMR and electron diffraction. X-ray diffraction of the silk nanoparticles shows that the nanoparticles crystallinity is about four fifths of the native fiber. Our results indicate that the degraded peptide chains of the regenerated silk is gathered homogeneously or heterogeneously to form a looser globular structure in aqueous solution. When introduced into excessive organic solvent, the looser globules of the liquid silk are rapidly dispersed and simultaneously dehydrated internally and externally, resulting in the further chain–chain contact, arrangement of those hydrophobic domains inside the globules and final formation of crystalline silk nanoparticles with β-sheet configuration. The morphology and size of the nanoparticles are relative to the kinds, properties and even molecular structures of organic solvents, and more significantly to the looser globular substructure of the degraded silk fibroin in aqueous solution. It is possible that the silk protein nanoparticles are potentially useful in biomaterials such as cosmetics, anti-UV skincare products, industrial materials and surface improving materials, especially in enzyme/drug delivery system as vehicle.  相似文献   

17.
We have used optical and EPR spectroscopy to study the mechanisms for color center formation in nanoporous glasses, polymethylmethacrylate, and alcoholic solutions containing ?-diketonate molecules: Cu(hfac)2, Ba(hfac)2, Pr(hfac)3, and Eu(fod)3. We have observed and studied the complex structure of the absorption bands in the 300 nm region belonging to the intraligand π-π* transition. Analogous results were obtained when studying the photoluminescence spectra of 5D07F0 transitions of Eu3+ ions and the EPR spectra of Cu2+ ions in matrices doped with Cu(hfac)2. We propose a model according to which for β-diketonate molecules (except for basic diketonates), a hydrolyzed form exists that is formed during synthesis of the polycrystalline powder due to the presence of water molecules. The model allows us to explain the spectral manifestations of β-diketonates in different matrices.  相似文献   

18.
The solid-state phase transitions of CuBr, CuI and NaNbO3 can be readily observed using 63Cu and 23Na high-temperature magic-angle spinning nuclear magnetic resonance spectroscopy. Temperature has large, linear effects on the peak maximum of 63Cu in each solid phase of CuBr and CuI, and there is large jump in shift across each phase transition. The 23Na MAS NMR peak intensities and the line widths in NaNbO3 also clearly show its high-temperature transition to the cubic phase. These data can be used to calibrate high-temperature MAS NMR probes up to 913 K, which is two hundred degrees higher than the commonly-used temperature calibration based on the chemical shift of 207Pb in Pb(NO3)2.  相似文献   

19.
Nuclear magnetic resonance (NMR) and relaxation of 63Cu and 65Cu in a powder sample of the heavy-fermion paramagnet CeCu6 is measured and analysed quantitatively. Five different Cu sites are accessible to a detailed analysis. We derive quadrupolar splitting frequencies, Ce to Cu transferred hyperfine field coupling constants, and transversal as well as longitudinal relaxation behaviour. Only small relaxation anomalies are observed at the orthorhombic to monoclinic structural phase transition of CeCu6. We point to the different importance of transferred hyperfine interaction and local conduction electron density for static or dynamic part, respectively, of Cu hyperfine interaction. The different sign of the transferred hyperfine interaction from Ce3+ to different Cu neighbours reveals the different competing interaction mechanisms, giving rise to the heavy-fermion paramagnetic behavior of CeCu6. Received 20 November 2001  相似文献   

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