Studies of dinucleoside monophosphates and monomer-polynucleotide interactions by proton magnetic resonance

The nature of the intra- and intermolecular base-stacking interactions involving several dinucleoside monophosphates in aqueous solution have been investigated by proton magnetic resonance spectrosocopy, and this method has been applied to a study of the interaction of polyuridylic acid with purine and adenosine monomers.

The pmr spectra of adenylyl (3' → 5') cytidine (ApC) and cytidylyl (3' → 5') adenosine (CpA) have been studied as a function of concentration and temperature. The results of these studies indicate that the intramolecular base-stacking interactions between the adenine and cytosine bases of these dinucleoside monophosphates are rather strong, and that the stacking tendencies are comparable for the two sequence isomers. The chemical shifts of the cytosine H₅ and adenine H₂ protons, and their variations with temperature, were shown to be consistent with stacked conformations in which both bases of the dinucleoside monophosphates are preferentially oriented in the anti conformation as in similar dApdC, and dCpdA (dA = deoxyadenosine; dC = deoxycytidine) segments in double helical DNA. The intramolecular stacking interaction was found to have a pronounced effect on the conformations of the ribose moieties, and these conformational changes are discussed. The concentration studies indicate extensive self-association of these dinucleoside monophosphates, and analysis of the concentration data facilitated determination of the dimerization constant for the association process as well as the nature of the intermolecular complexes.

The dependence of the ribose conformation upon the extent of intramolecular base-stacking was used to demonstrate that the base-base interaction in cytidylyl (3' → 5') cytidine (CpC) is rather strong, while there appears to be little interaction between the two uracil bases of uridylyl (3' → 5') uridine (UpU).

Studies of the binding of purine to several ribose and deoxyribose dinucleoside monophosphates show that the mode of interaction is base-stacking, and evidence for the formation of a purine-dinucleoside monophosphate intercalated complex is presented. The purine proton resonances are markedly broadened in this complex, and estimates of the purine linewidths in the complex and the equilibrium constant for purine intercalation are obtained.

A study of the interaction of unsubstitued purine with polyuridylic acid at 29°C by pmr indicated that purine binds to the uracil bases of the polymer by base-stacking. The severe broadening of the purine proton resonances observed provides strong evidence for the intercalation of purine between adjacent uracil bases of poly U. This interaction does not result in a more rigid or ordered structure for the polymer.

Investigation of the interaction between adenosine and polyuridylic acid revealed two modes of interaction between the monomer and the polymer, depending on the temperature. At temperatures above 26°C or so, monomeric adenosine binds to poly U by noncooperative A-U base stacking. Below this temperature, a rigid triple-stranded 1A:2U complex is formed, presumably via cooperative hydrogen-bonding as has previously been reported.

These results clearly illustrate the importance of base-stacking in non-specific interactions between bases, nucleosides and nucleotides, and also reveal the important role of the base-stacking interactions in cooperatively for med structures involving specific base-pairing where both types of interaction are possible.

I. The structure and properties of closed circular duplex DNA. II. Chemically interacting systems at equilibrium in a buoyant density gradient

I. The binding of the intercalating dye ethidium bromide to closed circular SV 40 DNA causes an unwinding of the duplex structure and a simultaneous and quantitatively equivalent unwinding of the superhelices. The buoyant densities and sedimentation velocities of both intact (I) and singly nicked (II) SV 40 DNAs were measured as a function of free dye concentration. The buoyant density data were used to determine the binding isotherms over a dye concentration range extending from 0 to 600 µg/m1 in 5.8 M CsCl. At high dye concentrations all of the binding sites in II, but not in I, are saturated. At free dye concentrations less than 5.4 µg/ml, I has a greater affinity for dye than II. At a critical amount of dye bound I and II have equal affinities, and at higher dye concentration I has a lower affinity than II. The number of superhelical turns, τ, present in I is calculated at each dye concentration using Fuller and Waring's (1964) estimate of the angle of duplex unwinding per intercalation. The results reveal that SV 40 DNA I contains about -13 superhelical turns in concentrated salt solutions.

The free energy of superhelix formation is calculated as a function of τ from a consideration of the effect of the superhelical turns upon the binding isotherm of ethidium bromide to SV 40 DNA I. The value of the free energy is about 100 kcal/mole DNA in the native molecule. The free energy estimates are used to calculate the pitch and radius of the superhelix as a function of the number of superhelical turns. The pitch and radius of the native I superhelix are 430 Å and 135 Å, respectively.

A buoyant density method for the isolation and detection of closed circular DNA is described. The method is based upon the reduced binding of the intercalating dye, ethidium bromide, by closed circular DNA. In an application of this method it is found that HeLa cells contain in addition to closed circular mitochondrial DNA of mean length 4.81 microns, a heterogeneous group of smaller DNA molecules which vary in size from 0.2 to 3.5 microns and a paucidisperse group of multiples of the mitochondrial length.

II. The general theory is presented for the sedimentation equilibrium of a macromolecule in a concentrated binary solvent in the presence of an additional reacting small molecule. Equations are derived for the calculation of the buoyant density of the complex and for the determination of the binding isotherm of the reagent to the macrospecies. The standard buoyant density, a thermodynamic function, is defined and the density gradients which characterize the four component system are derived. The theory is applied to the specific cases of the binding of ethidium bromide to SV 40 DNA and of the binding of mercury and silver to DNA.

Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

LiMn2-xGexO4 como material catódico para baterías de ión-litio

32 p.

Judd-Ofelt intensity parameters of Er3+ doped mixed alkali aluminophosphate glasses

Lithium sodium mixed alkali aluminophosphate glasses of the composition xNa(2)O-(15-x)Li2O-4B(2)O(3)-11Al(2)O(3)-5BaO-65P(2)O(5) (where x=0, 3.75, 7.5, 11.25 and 15 mol%) containing 0.5 mol% Er2O3 were prepared by melt quenching. The absorption spectra of Er3+ were studied from the experimental oscillator strengths and the Judd-Ofelt intensity parameters were obtained. The variations of Judd-Ofelt intensity parameters (Omega(2), Omega(4) and Omega(6)), experimental oscillator strengths of certain excited states of Er3+ and hypersensitive band positions with different mixed alkali content have been discussed in detail. It was found that there were similar effects of mixed alkali on both Judd-Ofelt intensity parameter 02 and the experimental oscillator strength of the hypersensitive transition, I-4(15/2) -> H-2(11/2). No shifts in the peak wavelength of the studied transitions were found in different glasses. (c) 2006 Elsevier B.V. All rights reserved.

Ag~+-Li~+离子交换制作Er~(3+)/Yb~(3+)共掺磷酸盐玻璃平面光波导(英文)

制备了化学稳定的Er^3＋／Yb^3＋共掺的磷酸盐玻璃，并在其中制作了用于光放大器和激光器的平面光波导．这种磷酸盐玻璃的失重速率为4．7×10^-5g·cm^-2·hr^-1，小于Kigre公司商业化的磷酸盐玻璃QX／Er的失重速率．采用Ag^＋-Li^＋交换技术制作了平面光波导并用m-线光谱在632．8nm测量了平面光波导的有效折射率．根据反WKB法得到折射率形貌，计算了离子交换参数如：离子交换深度、表面折射率，折射率改变和扩散系数等．

Helmholtz Fermi surface harmonics: an efficient approach for treating anisotropic problems involving Fermi surface integrals

We present a new efficient numerical approach for representing anisotropic physical quantities and/or matrix elements defined on the Fermi surface (FS) of metallic materials. The method introduces a set of numerically calculated generalized orthonormal functions which are the solutions of the Helmholtz equation defined on the FS. Noteworthy, many properties of our proposed basis set are also shared by the FS harmonics introduced by Philip B Allen (1976 Phys. Rev. B 13 1416), proposed to be constructed as polynomials of the cartesian components of the electronic velocity. The main motivation of both approaches is identical, to handle anisotropic problems efficiently. However, in our approach the basis set is defined as the eigenfunctions of a differential operator and several desirable properties are introduced by construction. The method is demonstrated to be very robust in handling problems with any crystal structure or topology of the FS, and the periodicity of the reciprocal space is treated as a boundary condition for our Helmholtz equation. We illustrate the method by analysing the free-electron-like lithium (Li), sodium (Na), copper (Cu), lead (Pb), tungsten (W) and magnesium diboride (MgB2)

不同退火气氛下γ-LiAlO2形貌和结构研究

研究了温度梯度法生长的γ-LiAlO2晶体在1100℃下富Li气氛和空气中退火处理后的表面形貌、表面结构以及吸收光谱。发现γ-LiAlO2晶体的抛光面在1100℃空气中退火后变为粗糙面，X射线衍射(XRD)分析表明此粗糙面为单相的LiAl5O8。而γ-LiAlO2晶体的抛光面在1100℃富Li气氛中处理后几乎没有变化。同时对不同气氛下热处理的γ-LiAlO2晶体进行了光谱分析，确认了晶片中196nm的吸收峰是由Li空位引起的。

新型衬底材料γ-LiAlO2热稳定性研究

研究了温度梯度法生长的γ-LiAlO2晶体在1100℃不同气氛处理的热稳定性。借助扫描电子显微镜和X射线衍射分析发现：1100℃／10h真空和空气处理后的样品表面分别形成了均匀微孔状和岛状LiAl5O8多晶；而富Li气氛处理后样品表面仍然光滑且仍为LiAlO2。用Leitz大视场显微镜观察重新抛光后样品内部宏观缺陷，发现空气和真空处理后样品缺陷增多，分别为岛状和条纹状缺陷；而富Li气氛处理后样品中缺陷明显减少。对比不同气氛处理的4块样品吸收光谱，确认了真空和空气处理产生的196nm吸收峰可能是Li空位吸收

大尺寸高质量γ-LiAlO2晶体的制备研究

采用提拉法快速（6mm／h）生长了透明、φ45mm×50mm完整的铝酸锂晶体，但晶体中下部出现了一个树状、乳白色的核芯．分别从透明和乳白色核芯部位取样，研磨作粉末X射线衍射测试，发现两个样品所有的衍射峰均可以用γ-LiAlO2指标化．双晶摇摆曲线显示晶体透明和乳白色部位的半高宽分别为116．9arcsec和132．0axcsec，结晶质量较差．通过三步气相传输平衡法（简称VTE）处理后，透明部位半高宽值（FWHM）降至44．2arcsec，乳白色部位FWHM值降至53．3arcsec．结合快速生长和VTE

Structural, optical and electrical properties of ZnO films grown on c-plane sapphire and (100)gamma-LiAlO2 by pulse laser deposition

ZnO thin films were grown on single-crystal gamma-LiAlO2 (LAO) and sapphire (0001) substrate by pulsed laser deposition (PLD). The structural, optical and electrical properties of ZnO films were investigated. The results show that LAO is more suitable for fabricating ZnO films than sapphire substrate and the highest-quality ZnO film was attained on LAO at the substrate temperature of 550 degrees C. However, when the substrate temperature rises to 700 degrees C, lithium would diffuse from the substrate (LAO) into ZnO film which makes ZnO film on LAO becomes polycrystalline without preferred orientation, the stress in ZnO film increases dominantly and the resistivity of the film decreases exponentially. (c) 2005 Elsevier B.V. All rights reserved.

Influence of vapor transport equilibration on the crystal quality and thermal-expansion coefficients of gamma-LiAlO2

gamma-LiAlO2 (LAO) single crystal has been grown by the Czochralski method. However, its quality was deteriorated due to lithium volatilization during the crystal growth. The full width at half maximum value drops from 116.9 to 44.2 arc sec after the LAO slice was treated by vapor transport equilibration at 1000, 1100, and 1200 degrees C/48 h in sequence. The treated slice shows higher optical transmission than the as-grown one in the measured wavelength range of 190-1900 nm, meanwhile, its absorption edge exhibits a blueshift. According to Raman spectra, the treated slice has homogeneous quality at different depths from surface to 0.01 mm. The expansion coefficient of the treated slice for a axis drops from 17.2398x10(-6)/degrees C to 16.5240x10(-6)/degrees C, and that for c axis drops from 10.7664x10(-6)/degrees C to 10.0786x10(-6)/degrees C.

Spectra analysis of a novel Ti-doped LiAlO2 single crystal

LiAlO2 single crystals doped with Ti at concentration 0.2 at.% are grown by the Czochralskl technique with dimensions Phi 42 x 55 mm. Ti ions in the crystal are quadrivalence proven by comparing the absorption and fluorescence spectra of pure LiAlO2 and Ti: LiAlO2. After air and Li-rich atmosphere annealing, the absorption peaks in the range of 600-800nm disappear. We conclude that 682 and 756nm absorption peaks are attributed to the V-Li and V-O absorptions, respectively. The peaks at 716nm and 798nm may stem from the V-Li(+) and F+ absorptions. The colour-centre model can be applied to explain the experimental phenomena. Ti4+-doping produces more lithium vacancies in the LiAlO2 crystal. The intensities of [LiO4] and the associated bonds remain unchanged, which improves the anti-hydrolyzation and thermal stability of LiAlO2 crystals.

高浓度掺Er^3＋铌酸锂晶体的光谱参数计算

用提拉法成功地生长了6mol％的高浓度掺铒铌酸锂晶体。测量了晶体的两个非偏振方向（X和Z）以及两个偏振方向（π和δ）的吸收光谱。高浓度掺铒铌酸锂晶体的吸收系数高，有利于提高泵浦效率。根据所测的吸收光谱用Judd-Ofelt理论拟合出了Er^3＋离子的强度参数Ωλ。所得的均方差结果显示偏振拟合的误差要小于非偏振拟合。利用偏振吸收数据计算了各能级跃迁的自发辐射跃迁几率（AJJ’）、辐射寿命（τ）、荧光分支比（β）和积分发射截面（σp）等参数，对计算结果进行了讨论并与其他文献的报道结果进行了比较。

Influence of LiB3O5 structure on microstructure and optical properties of ZrO2, thin films prepared by electron beam evaporation

ZrO2 thin films were deposited bill using an electron beam evaporation technique on three kinds of lithium triborate (LiB3O5 or LBO) substrates with the surfaces at specified crystalline orientations. The influences of the LBO structure on the structural and optical properties of ZrO2 thin films are studied by spectrophotometer and x-ray diffraction. The results indicate that the substrate structure has obvious effects on the structural end optical properties of the film: namely. the ZrO2 thin film deposited on the X-LBO, Y-LBO and Z-LBO orients to m(-212), m(021) and o(130) directions. It is also found that the ZrO2 thin film with m(021) has the highest refractive index and the least lattice misfit.