Dissolution of cellulose in aqueous NaOH/urea solution: role of urea

Urea can improve the solubility and stability of cellulose in aqueous alkali solution, while its role has not come to a conclusion. To reveal the role of urea in solution, NMR was introduced to investigate the interaction between urea and the other components in solution. Results from chemical shifts and longitudinal relaxation times show that: (1) urea has no strong direct interaction with cellulose as well as NaOH; (2) urea does not have much influence on the structural dynamics of water. Urea may play its role through van der Waals force. It may accumulate on the cellulose hydrophobic region to prevent dissolved cellulose molecules from re-gathering. The driving force for the self-assembly of cellulose and urea molecules might be hydrophobic interaction. In the process of cellulose dissolution, OH^? breaks the hydrogen bonds, Na⁺ hydrations stabilize the hydrophilic hydroxyl groups and urea stabilizes the hydrophobic part of cellulose.     

图解中心原子轨道的杂化方式

借助图形方法,分析了不同常见几何构型分子中心原子轨道杂化方式的原因——与端基原子轨道的有效重叠,利用中心原子价层轨道的能量接近度的判断,决定最终可能的杂化方式。     

橡胶高弹性大形变的唯象理论

通过简单的假定,由纯粹的数学论证推导出橡胶高弹性的储能函数公式,在橡胶大形变时,公式比统计理论的更能反映客观实际。     

Comparison Studies on Several Ligands Used in Determination of Cd(II) in Rice by Flame Atomic Absorption Spectrometry after Ultrasound-Assisted Dispersive Liquid–Liquid Microextraction

Ligands plays an important role in the extraction procedures for the determination of cadmium in rice samples by using flame atomic absorption spectrometry (FAAS). In the present study, comparative evaluation of 10 commercially available ligands for formation of Cd(II)-ligand complex and determination of cadmium in rice samples by ultrasound-assisted dispersive liquid–liquid microextraction (UADLLME) combined with FAAS was developed. Sodium diethyldithiocarbamate (DDTC) provided a high distribution coefficient as well as a good absorbance signal, therefore DDTC was used as a ligand in UADLLME. A low density and less toxic solvent, 1-heptanol, was used as the extraction solvent and ethanol was used as the disperser solvent. In addition, the experimental conditions of UADLLME were optimized in standard solution first and then applied in rice, such as the type and volume of extractant and dispersant, pH, extraction time, and temperature. Under the optimal experimental conditions, the detection limit (3σ) was 0.69 μg/L for Cd(II). The proposed method was applied for the determination of Cd(II) in three different rice samples (polished rice, brown rice, and glutinous rice), the recovery test was carried out, and the results ranged between 96.7 to 113.6%. The proposed method has the advantages of simplicity, low cost, and accurate and was successfully applied to analyze Cd(II) in rice.     

一种经MCM-41负载双齿膦钯(0)配合物催化的羰基化Suzuki偶联合成二芳酮的新途径

在催化量的MCM-41负载双齿膦钯(0)配合物存在下,芳基碘化物和芳基硼酸、一氧化碳在常压下能顺利进行羰基化Suzuki偶联反应,高产率地生成了各种二芳酮化合物。MCM-41负载双齿膦钯(0)配合物具有比PdCl2(PPh3)2 更高的活性和选择性,且可回收再用10次其活性基本不变,为各种功能化二芳酮的合成提供了方便实用的新途径。     

双核烷基咪唑过氧磷钨酸盐相转移催化剂合成及催化烯烃环氧化性能

合成并表征了一类双核长链烷基咪唑阳离子修饰的过氧磷钨杂多酸盐催化剂[Dnmin]1.5PW4O24,考察了催化剂在过氧化氢为氧源的烯烃环氧化反应中的催化活性.研究表明,这类催化剂在反应过程中表现出相转移催化现象,并具有较高的催化活性和选择性.其中,双核十二烷基咪唑杂多酸盐催化剂[D12min]1.5PW4O24的活性最佳,其环己烯转化率和环氧环己烷选择性分别达到97.7%和96.3%.催化剂在经过简单离心分离后可重复使用,重复使用4次后环己烯转化率和环氧环己烷选择性仍可分别达到72.4%和97.2%.催化剂[D12min]1.5PW4O24在其它几种烯烃的环氧化反应中均表现出相转移催化特性,且具有较高的催化活性.     

Rare earth‐doped calcium‐based magnetic catalysts for transesterification of glycerol to glycerol carbonate

Several rare earth‐doped, calcium‐based magnetic catalysts were prepared for the synthesis of glycerol carbonate. The basicity and basic strength analysis of the catalysts showed that the doping of rare earth improved the basicity of the catalysts, and the doping of lanthanum maximized it. In addition, with the doping of lanthanum, the particle size of the catalyst became smaller to promote the organic reactants near the active sites of catalysts, thereby effectively improving the performance. NiFe₂O₄@[CaO‐La₂O₃] shows better catalytic performance with 99.0% yield of glycerol carbonate compared to the other catalysts. The NiFe₂O₄@(CaO‐La₂O₃) could be reused in six cycles without significant loss in activity.     

联萘酚多氢键硫脲催化合成1,4-二氢吡啶衍生物

本文合成了三种具有多氢键的联萘酚轴手性硫脲催化剂,并将其用于催化合成1,4-二氢吡啶衍生物。结果显示,所合成的新型多氢键硫脲均表现出较好的催化作用,能有效地提高1,4-二氢吡啶衍生物的收率和对映选择性。所有新化合物结构均经过~1H NMR、~(13)C NMR、IR、熔点等表征所确认。     

碳酸钙固硫固体进样测汞仪快速测定硫化铅精矿中汞

在使用固体进样测汞仪直接测定硫化铅精矿中汞时,由于试样中硫含量通常较高(高达30%以上),在测定过程中大量的硫被氧化会污染甚至腐蚀固体进样测汞仪的核心部件催化管,导致催化管寿命严重缩短。为解决该问题,建立碳酸钙固硫-固体进样测汞仪直接测定硫化铅精矿中汞的分析方法;并对Ca/S比,分解温度,分解时间,齐化时间等参数进行优化。在最优条件下,Hg的含量在2~20 ng和20~500ng线性范围内回归系数(R²)分别为0.9996和0.9998;方法检出限(LOD)为0.006 μg/g。用该法对3个典型样品进行测定,相对标准偏差RSD≤9%(n=7),加标回收率为96%~106%。该方法简单、快捷,准确度和精密度高,适合硫化铅精矿中汞的快速测定。     

A GENERALIZED RESULT ON THE POLYNOMIAL-LIKE ITERATIVE EQUATION

Most results on the polynomial-like iterative equation are given under the condition that the given function is monotone,while a work by L.Liu and X.Gong gets nonmonotone PM solutions with height 1 when the given function is of the same case.Removing the condition on height for the given function,we first give a method to assert the nonexistence of C⁰solutions,then present equivalent conditions for the existence of PM solutions with finite height.Finally,as an application of the equivalent conditions,we construct the PM solutions in the case that the given function has one fort.