NaOH-Na2H2SiO4-H2O体系渗透系数的等压法测定及离子作用模型

采用等压法测定了313.15 K下NaOH-Na₂H₂SiO₄-H₂O体系在0.5695～6.4775 mol•kg^－1的离子强度范围及0.1461～0.3158的模数(SiO₂与Na₂O的物质的量比)范围内的等压平衡浓度, 计算了该混合体系的渗透系数和水活度. 用Pitzer离子相互作用模型对实验结果进行了参数化研究, 拟合求取了Pitzer离子相互作用参数. 用Pitzer模型计算的渗透系数值与实验结果一致, 说明该模型能较好的描述NaOH-Na₂H₂SiO₄-H₂O体系的热力学性质. 用Pitzer模型计算得到了该体系的各组分平均活度系数随离子强度及模数的变化规律, 并与Mckay-Perring方程计算得到的NaOH的平均活度系数进行了比较, 指出Mckay-Perring方程的适用性.     

高温高压下NaCl-CaCl2-H2O体系Raman光谱的定量研究

三元体系NaCl-CaCl₂-H₂O是一种重要的天然水-盐体系。然而,研究人员在过去只研究了低温下该体系的相变,但在高温高压条件下拉曼位移和物理参数之间的定量关系却并没有被报道。利用利用热液金刚石压腔(HDAC)和石英压标,对高温高压下三元体系NaCl-CaCl₂-H₂O的拉曼光谱特征进行了系统的研究,并获得了水的O—H伸缩振动谱带的拉曼位移、溶质质量分数和压力之间的定量关系。其中盐的质量分数相等(NaCl与CaCl₂),分别为4.0 mass％,8.0 mass％和12.0 mass％。实验结果表明,当盐的质量分数和体系的压力保持不变时,O—H伸缩振动的标准拉曼位移差(Δν_(O—H))伴随着温度的升高而增大。当温度和压力恒定时,Δν_(O—H)随盐的质量分数的增加而增大。对于这个三元体系,其Δν_(O—H)与压力近似为线性关系,且不同盐度条件下的关系斜率相近。Δν_(O—H)与温度(T)、压力(P)、溶质质量分数(M)之间的定量关系为P＝-31.892Δν_(O—H)+10.131T+222.816M-3 183.567,其中该方程的有效PTM范围为200 MPa≤P≤1 700 MPa, 273 K≤T≤539 K 以及M≤12 mass%。该公式可以用来作为地质压力计,用于研究等盐度条件下在NaCl-CaCl₂-H₂O体系流体包裹体。该方法作为一种直观的地质探测技术,具有潜在的应用价值。     

荒漠-绿洲交错地带典型植被光谱特征研究

植被对区域生态环境保护具有重要意义,尤其是在荒漠-绿洲交错地带,植被对土壤保持、提高土地的抗剪切性能有重要意义,对土壤风蚀和荒漠化防治的影响作用较大,利用高光谱技术测定并分析荒漠-绿洲交错带典型植被的光谱特性,不仅能够指导区域的植被遥感分类,还能够对植被实行远程监控提供依据。研究借助美国Field Spec 4高分辨率地物光谱仪,在研究区采集棉花、柽柳、梭梭和盐穗木等四种典型植被不同条件下的光谱数据,在对数据进行归类、筛选及综合处理后,分别对原始数据进行FDR(一阶导数反射率)和RLR(倒数取对数反射率)变换。利用原始数据、FDR和RLR分别分析不同植物的光谱敏感波段和表达方式。结果表明：植物的光谱曲线具有类似的变化特征,植被种类不同在“红边”区和近红外780～1 260 nm波段的表达方式区别较大;植物对可见光的吸收非常强烈,对不同波长的光吸收强弱变化会形成波峰和波谷;植物红边特征具有特殊性,蕴含植物自身的特有信息,三种方式的处理结果显示,光谱特征在经FDR计算后,植物光谱红边特征区差异性非常明显;利用三种不同方式处理后的光谱数据,分别来计算改进的植物NDVI值,经RLR变换后重新计算得到的NDVI值在植物不同种之间表现出较大差别,用于植物种类区分的效果明显。     

一种基于HLLC算法的Mie-Grüneisen多介质混合模型

建立一种修正的HLLC （Harten-Lax-Van Leer-Contact）格式下稳定的Mie-Grüneisen多介质混合计算模型.Mie-Grüneisen混合模型中的通量包括守恒和非守恒两个部分,原始的HLLC格式对守恒部分适用,但是原始的HLLC格式直接用于非守恒部分,很难控制住数值振荡的产生.在原始格式中,间断面的移动速度为间断网格的左侧或右侧速度,修正后替换为网格中的平均速度,经过修正后,对HLLC格式重新进行推导,并随之扩展到二维问题.数值实验表明,利用修改后的HLLC格式,Mie-Grüneisen混合模型可以取得较好的稳定性和准确性.     

Sulfinate‐Salt‐Mediated Radical Relay Cyclization of Cyclic Ethers with 2‐Alkynylbenzonitriles toward 3‐Alkylated 1‐Indenones

A new sulfinate salt‐mediated radical relay for the completion of C(sp³)?H bond indenylation of cyclic ethers with readily available 2‐alkynylbenzonitriles by combining silver/tert‐butyl peroxide (TBHP) was established, providing a wide range of 3‐alkylated 1‐indenones with generally good yields. Interestingly, the current reaction system can tolerate an S‐centered radical and a C‐centered radical in one pot, in which the S‐centered radical promotes the formation of the C‐centered radical to induce a radical cascade without disturbing the reaction process. A reaction mechanism is also proposed based on control experiments.     

Structure of azadirachtin-I, 11 β-H epimer

The 11 -H epimer of Azadirachtin-I, isolated from the seed kernels of Azadirachta indica A. Juss (Neem), was characterized by both NMR and X-ray crystallographic techniques. NMR data reveals that the H11 proton is in -orientation and the X-ray studies confirm this observation. The compound crystallized in space group P2₁ with the cell parameters a = 11.933(2) Å, b = 7.752(5) Å, c = 17.241(9) Å, = 106.80(3). Though the structural features are similar to the 11 -H epimer of Azadirachtin-H, the orientation of the acetoxy group at C3 is different. The dihedral angle C9–C8–C14–O13, which describes the relative orientation of the modified decalin and modified furan moities of the molecule, is 23.3(8).     

Systematic investigation of hydrogen storage properties in RNi5-H (R = rare earth) systems

We investigated hydrogen storage properties in RNi₅-H (R = rare earth) systems. Pressure-composition isotherms showed that a single pressure plateau separates into two plateaus (lower and higher plateau) as the atomic number of Relement in RNi₅-H systems increases, indicating the presence of two hydrides. In higher-number RNi₅-H systems, both plateaus disappear, while another pressure plateau related to a novel hydride appears at low hydrogen content. The decrease of the unit cell volume due to the lanthanide contraction leads to the instability of hydrogen, suggesting an increase in both the lower and higher plateau pressures.     

Alumina-supported heteropoly acid: An effi cient catalyst for the synthesis of azaarene substituted 3-hydroxy-2-oxindole derivatives via C(sp3)H bond functionalization

A method of C(sp3)-H bond functionalization of methyl azaarenes catalyzed by alumina-supported heteropoly acid and addition to isatins was developed. This transformation could be used for the synthesis of biologically important 3-hydroxy-2-oxindole derivatives in good to excellent yields and the catalyst could be reused for six times without significant decrease in activity.     

Thermally-Induced Intramolecular [4+2] Cycloaddition of Allylamino- or Allyloxy-Tethered Alkylidenecyclopropanes

A thermally-induced intramolecular [4+2] cycloaddition reaction of allylamino- or allyloxy-tethered alkylidenecyclopropanes has been reported in this paper, giving a new protocol for the rapid construction of polycyclic skeleton molecules in moderate to excellent yields with a broad substrate scope. On the basis of control experiments and DFT calculations, we disclosed that the reaction proceeded through a [4+2] cycloaddition and trace of water assisted 1,3-H shift process to give the target product.     

现代高分子物理课程系列漫谈——溶液中高分子单链自由能

针对休克尔分子轨道(HMO)理论中只考虑相邻原子轨道相互作用的缺点,提出了一种改进的HMO模型,明确考虑间位碳原子共振积分,采用对称性匹配的分子轨道,得到了π共轭体系的能级公式,发现分子对称性降低可产生额外稳定化能,从而正确解释了纯碳环C2n分子稳定结构中键角交替变化规律,为理解二级Jahn-Teller效应提供了新思路。