碱木素的近红外光谱吸收机理的研究

通过碱木素模型物对醌、邻醌和香兰素的溶液在800～900 nm的近红外光谱波段内的吸收谱图的对比发现,对醌和邻醌在此波段产生较强的吸收,而香兰素基本上没有吸收,证明了碱木素的醌型结构在800～900 nm波段内产生特征吸收。对银杏和夹竹桃磨木木素碱处理前后的溶液在800～900 nm波段内的吸光度的差别分析,发现夹竹桃的磨木木素的吸光度的相对变化更大,这是由于夹竹桃磨木木素经碱处理后产生了更多的醌型结构。这也是在硫酸盐法蒸煮过程中在800～900 nm波段内阔叶材的蒸煮液吸光度大于针叶材的蒸煮液吸光度的主要原因。     

密度泛函理论研究碱金属原子在完美氧化镁(001)表面的吸附

基于平面波赝势法的密度泛函理论系统地研究了孤立碱金属原子(锂、钠、钾、铷、铯)在完美氧化镁(001)表面的吸附. 锂在氧位表面上的吸附能是0.72 eV,大约是其它碱金属的3倍. 锂和表面氧之间较强的相互作用主要是来源于共价键的作用,这可由态密度和差分电荷密度的分析所证实. 讨论碱金属在MgO(001)表面吸附的成键机理.     

碱熔试样-原子吸收光谱法测定铜阳极泥预处理渣料中的Sb

铜阳极泥是一种重要的冶金工业副产品,因其中含有多种贵金属和有价金属元素,铜阳极泥的综合回收利用日益受到关注。铜阳极泥预处理富集渣中富含的Sb难以用常规方法溶解,有必要建立一种准确、简便的测试方法实现Sb的定量分析。采用X射线荧光光谱、X射线衍射光谱和场发射扫描电镜能谱分析等多种光谱学分析手段对富集渣的化学成分、物相和微观结构做了全面分析,结果表明,富集渣的化学组成和物理结构复杂,组分化学性质稳定且共生紧密。Sb以高锑酸金属化合物的形式存在,结构稳定化学惰性强。采用Na₂O₂熔融法消解试样,合成标准样品做标准系列,用火焰原子吸收光谱法测定了富集渣中Sb的含量值为8.23%,相对标准偏差为0.97%。该方法的检出限为0.072%,加标回收率为94.9%~99.2%。本方法溶样彻底,不需贵重试剂和仪器,方法简单易行。采用与样品基体相近的合成标准样品,消除了样品化学成分复杂所造成的共存物质干扰。通过标准样品测试验证和其他仪器方法比对,证明本方法灵敏度高,准确性好,可用于铜阳极泥预处理渣料中Sb的定量测定。     

Microscopic Study of the Rock Salt-Caesium Chloride Phase Stability in Alkali Halides

In this work we present a microscopic study of observable magnitudes linked to the relative stability of the rock salt (B1) and caesium chloride (B2) phases in the AX (A: Li, Na, K, Rb, Cs; X: F, Cl, Br, I) crystal family. Transition pressures and j Y = Y ( B 2) m Y ( B 1) differences in total energies, volumes, and bulk moduli at zero and transition pressures are computed following a localized Hartree-Fock scheme. The arrangement of the data in clear trends is shown to be dominated by the cation atomic number, being weaker the dependence of the data on the anion. These systematics are well interpreted in terms of a variety of microscopic arguments that emerge from the decomposition of the energy, pressure, and bulk modulus in anionic and cationic contributions.     

Electronic properties of self-assembled quantum dots of sodium on Cu(1 1 1) and their interaction with water

The electronic properties of thin films of Na on Cu(1 1 1) and their interaction with water have been investigated at room temperature by high resolution electron energy loss spectroscopy. The first Na layer is characterized by two features tentatively assigned to charge density waves. The second Na layer grows as small islands. The loss spectrum of this layer shows a feature at 3.0 eV identified as a Mie resonance. Increasing alkali coverage, Na islands form a continuous film, as indicated by the appearance of a Na surface plasmon and by the disappearance of the Mie resonance. Water vapour strongly interacts with Na layers as shown by the OH-Na vibration whose frequency shifts from 36 meV to 53 meV as a function of alkali coverage.     

General axial shapes of sodium clusters

The shell correction method is applied to calculate the shapes and binding energies of Na clusters. The axial equilibrium shapes are calculated by minimizing five deformation parameters simultaneously. Strong deviations from spheroidal shapes including reflection asymmetric ones are found. The influence of cluster deformation on the separation energies and ionization potentials and on the splitting of the photo - resonance are compared with the available experimental data. The N-dependence of the cluster shape and its relation to the N- and Z-dependences of the nuclear shape is discussed.     

固体和熔融碱金属碳酸盐的Raman光谱研究

用高温共焦显微激光 Raman光谱仪测定了不同温度下固体和熔融态的碳酸钠、碳酸锂以及不同成份的固态和液态 Li2 CO3- Na2 CO3混合物的 Raman光谱图 ,分析了 Na+和 Li+对碳酸根离子作用力的变化。根据 CO32 -对称伸缩振动模的波数移动情况 ,在固态混合物中也发现了混合效应     

A 125Te and 23Na NMR investigation of the structure and crystallisation of sodium tellurite glasses

125Te static nuclear magnetic resonance (NMR) and 23Na and 125Te magic angle spinning (MAS) NMR have been used, in conjunction with X-ray diffraction, to examine the structure and crystallisation behaviour of glasses of composition xNa2O.(1-x)TeO2 (0.075 x 0.4). The MAS NMR 23Na spectra from the glasses are broad and featureless but shift by approximately +5 ppm with increased x, i.e. as the system becomes more ionic. The static 125Te NMR spectra show an increase in axial symmetry with increasing x, indicating a shift from predominantly [TeO4] to [TeO3] structural units. The 23Na and 125Te spectra from the crystallised samples have been fitted to obtain information on the sites in the metastable crystal phases, which are the first to form on heating and which are therefore more closely related to the glass structure than thermodynamically stable crystal phases. New sodium tellurite phases are reported, including a sodium stabilised, face centred cubic phase related to delta-TeO2; a metastable form of Na2Te4O9 containing 3 sodium and 4 tellurium sites; and a metastable form of Na2Te2O5 containing 2 sodium sites. There is evidence of oxidation of TeIV to TeVI occurring in glasses with high values of x and, at x=0.40 and 0.50 (outside the glass forming range), some sodium metatellurate (Na2TeO4) is formed at the same time as sodium metatellurite (Na2TeO3). The 125Te shift is very sensitive to environment within the sodium tellurite system, covering more than 320 ppm, with anisotropies varying from 640 to 1540 ppm. The lack of features in the 125Te spectra of the glass phases, combined with the large shift range and high but variable anisotropy, means than it is not possible to obtain a unique fit to any presumed species present. Furthermore, the chemical shift anisotropy parameters for three of the four Te sites in the Na2Te4O9 phase are found to lie outside the range used for previous simulations of glass spectra.     

Charge-Transfer Processes in Doped Alkali Halides

Defects formation under UV-irradiation in the impurity-induced absorption bands at 4.2 K has been studied for crystals with and without traps for electrons (CsI:Pb and Eu^2?-doped alkali halides, respectively). In both cases the results have been explained by an electron transfer from the impurity-perturbed halogen ion states, resulting in the appearance of electrons and holes in the crystal. In CsI:Pb, the electrons are trapped by lead ions and the holes are self-trapped. In Eu^2?-doped crystals, the electrons and the holes recombine with the formation of excitons, whose decay results in the creation of Frenkel defects.     

Investigation of Inelastic Light Scattering in Heavily Electron-Irradiated Alkali Halides

The properties of several unusual Raman scattering peaks observed in heavily irradiated NaCl with vast amounts of colloidal sodium are investigated. A new peak (at 3580 cm^?1) has been observed far beyond the cut-off limit of the one-phonon spectrum. This scattering phenomenon has been explained with an electron quantum confinement model where the electronic excitations are quantized as expected for wire-like structures of nano-particles of metallic sodium.     

Alkali displacements in intercalated 1T-TaSe2

Single crystals of 1T-TaSe₂ have been intercalated with different alkali metals by deposition in ultra-high vacuum onto in situ-cleaved (0001) surfaces. In a second step a different alkali metal, or Cl₂, has been deposited on top. The interactions among the deposited species and the substrate have been investigated using soft x-ray photoelectron spectroscopy (SXPS). Li and Na appear to compete in the intercalation process. Li replaces Na, by pushing it deeper into the crystal. Cs on Li:TaSe₂ does not intercalate, but stays on top, repelling intercalated Li⁺ deeper inside. For Li on Cs:TaSe₂ an exchange reaction takes place, and Cs is deintercalated. The same effect is induced by Na deposited on intercalated Cs. 1T→2H phase transition for TaSe₂ has been observed only for Li deposition. Cl₂ deposition on Na intercalated substrate induced deintercalation of Na. The experimental results are discussed in relation to thermodynamic, electronic and electrostatic effects. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

碱蓝6B共振光散射法检测DNA

研究了碱蓝 6B与脱氧核糖核酸在酸性条件下共振光散射特征 ,考察了影响因素和最佳反应条件 ,建立了一种测定纳克级DNA的方法。在四硼酸钠 盐酸 (pH =2 90 )缓冲溶液中 ,线性范围为 10～ 10 0 4 μg·L- 1 ,相关系数为 0 9913,检出限为 4 2 μg·L- 1 ,用于合成样品的测定结果令人满意。     

含硼分子筛的11B VAS NMR和1H MAS NMR研究

以变角旋转(VAS) NMR方法考察了三配位硼的存在状态,得到其四极作用常数C_q为2.4MHz,电场梯度不对称系数η为0.0.硼引入骨架形成的酸性羟基质子的信号位于2.3ppm,¹H{¹¹B}双共振实验证实其与硼原子的关联很弱.与6.5ppm分子筛吸水峰同时出现的2.7ppm的信号也被认为是吸水的信号,与非骨架铝羟基质子的信号在同一位置,但可通过¹H{²⁷Al}双共振实验加以判别.     

Alkali metal emissions in an early-stage pulverized-coal flame: DNS analysis of reacting layers and chemistry tabulation

The intricate coupling between coal pyrolysis, gas phase combustion and the emissions of alkali metal, such as sodium, is studied in the early stage of a temporally evolving three-dimensional planar turbulent jet carrying pulverized-coal particles. Complex chemistry is used to account for both the combustion of volatile hydrocarbons and the sodium containing species. The response of the sodium chemistry is analyzed in the mixture fraction space, along with the topology of the reactions zones. Combustion is found to start preferentially in partially premixed flames, which then evolve toward diffusion-like reactive layers and reach chemical equilibrium. From the direct numerical simulation (DNS) database, the possibility of modeling the dynamics of sodium species using one-dimensional premixed flamelet generated manifolds (FGM) is investigated. A chemical lookup table is constructed for the combustion of the partially premixed volatiles and an additional three-dimensional simulation is performed to compare the tabulated sodium species against their reference counterparts with complex chemistry. Quantitative analysis of the performance of the developed chemistry tabulation confirms the validity of the approach. Perspectives for the modeling of sodium emissions in pulverized-coal furnaces and boilers are finally drawn.     

Spectroscopic Study of Some Alkali and Alkaline Earth Complexes with Benzo Crown Ethers in Ethanol Solution

The interaction between Na⁺, K⁺, Mg²⁺ and Ca²⁺ ions and benzo crown ethers B15C5, DB18C6, DB21C7, DB24C8 and DB30C10 in ethanol solution has been studied spectrophotometrically at 25°C. The formation constants for 1:1 complexes were determined by computer fitting of the resulting UV-absorbance-mole ratio data. In the case of all crown ethers used, K⁺ ion was found to form the most stable complexes. The observed selectivities of different benzo crowns for the cations used are discussed in terms of the cavity-cation size ratio, number of the donating oxygens participating in the cation binding, conformations of the free and complexed ligands and ionic solvation.     

A Multi-Frequency EPR and ENDOR Study of Rh and Ir Complexes in Alkali and Silver Halides

Aliovalent Rh and Ir cations have been frequently used to influence the photographic properties of silver halide emulsions. The doping introduces several types of related defects with distinct trapping and recombination properties. EPR and ENDOR are, in principle, ideally suited for the determination of the microscopic structure of the individual centres but it will be demonstrated that well-chosen, sometimes sophisticated multi-frequency experiments are necessary in order to (partially) reach this goal. Model studies on single crystals of AgCl and NaCl also appeared indispensable for the unravelling of the spectra.

In the review of Rh-centres in NaCl and AgCl special attention is paid to methods that allow to detect cation vacancies near Rh^2? complexes. An alternative explanation for the high temperature behaviour of the [RhCl₆]^4? complexes in AgCl is presented.     

Sodium adsorption on a Ge(100)-(2 × 1) surface

The adsorption of Na on a Ge(100)-(2 × 1) surface has been studied by means of AES, LEED, EELS, TPD and work-function measurements. In the submonolayer coverage region the coverage dependencies of the desorption activation energy E(Θ) and desorption frequency v(Θ) have been determined using the threshold TPD method. Our experimental data show that after the completion of the first Na layer, 3D crystallites develop on the Na/Ge(100) surface (Stranski-Krastanov growth mode). For Θ > 1 ML, formation, followed by decomposition of a certain Na---Ge surface compound occurs in the temperature range 410–550 K.     

Effects of Na and K co-doping on growth and scintillation properties of Eu:SrI2 crystals

We grew Na and K co-doped Eu:SrI₂ [Na,Eu:SrI₂ and K,Eu:SrI₂] crystals by a modified micro-pulling-down method to reveal the co-doping effects on the crystal growth and scintillation properties. The non-codoped, Na0.5%, Na1.0%, K0.5% and K1.0%,Eu:SrI₂ crystals indicated high transparency while the milky parts were generated in the Na5.0% and K5.0%,Eu:SrI₂ crystals. The light yields of Na,Eu:SrI₂ and K,Eu:SrI₂ crystals under γ-ray irradiation were decreased by the Na and K co-doping. On the other hand, there was a small change within 940–1020 ns in the decay times by the Na and K co-doping. In the light yield proportionality under γ-ray irradiation, the non-proportionality in the low energy region was improved by Na and K co-doping.     

Alkali metal adsorption on graphite: Calculation of a work function variation in the Anderson-Newns-Muscat model

Within the scope of the Anderson-Newns model of adsorption the Na, K, and Cs submonolayer films on graphite are considered. The adatoms dipole-dipole repulsion is taken into account with the use of the Muscat approach. The calculated work function variations are in a reasonable agreement with the experimental data. We have found that the charges of K, Na, and Cs adatoms are Z₀ = 0.22, 0.38, and 0.41 for the zero coverage limit and Z_ML = 0.09, 0.15, and 0.16 for the monolayer coverage correspondingly. The crude estimations of the single adatom binding energies got E_b = 0.76, 0.67, and 0.37 eV for Na, K, and Cs accordingly.     

Properties of Hydrated Alkali Metals Aimed at the Ion Channel Selectivity

The hydration structure properties of different alkali metal ions with eight water molecules and potassium ions with different numbers of water molecules are studied using the mixed density functional theory, B3LYP, with 6-3110 basis set. The hydration structures are obtained from structure optimization and the optimum numbers of water molecules in the innermost hydration shell for the alkali metal ions are found. Some useful information about the ion channel selectivity is presented.