N,N,N,′N′-四丁基丁二酰胺的合成及其萃取稀土离子Pr(Ⅲ)的研究

合成了四取代双酰胺萃取剂N,N,N,′N′-四丁基丁二酰胺(TBSA),并对萃取剂的结构进行了表征。研究了其萃取Pr(Ⅲ)的性能,考察了硝酸浓度、萃取剂浓度、硝酸锂浓度以及温度等对萃取分配比的影响。萃取反应在298K时,TBSA以甲苯为稀释剂时的热力学焓变为-12.83 kJ/mol。萃合物的组成结构为Pr(NO3)3.3TBSA。     

Thermodynamics and dynamics of metallic glass formers: their correlation for the investigation on potential energy landscape

Great progress has been made in basic features of the potential energy landscape (PEL) theoretically. The present work, however, attempts to cast new light on it from experimental aspects. By a survey of experimental data related to thermodynamics or dynamics of metallic glass-forming liquids, it is found that the increased rate of excitation of vibrational entropy at glass transition tends to increase the rate of generation of configurational part. Although for the type of metallic materials a generally positive relationship exists between the density of the energy minima at glass transition and the liquid fragility strength, just as expected, our main attention is paid to the phenomenon of the scattering of the slopes. Analysis shows that the phenomenon results from the different average height of energy barriers between minima near glass transition. Investigation on the PdNiP metallic system indicates that the mismatch entropy is a dominant factor in the barrier height: a large value of it results in low energy barriers. Our previous work on the AlNiCe system gives the support to this finding.     

Fluorescence and aggregation behavior of poly(amidoamine) dendrimers peripherally modified with aromatic chromophores: the effect of dendritic architectures

PAMAM dendrimers of the zeroth to fifth generation (G0-5) have been peripherally modified with phenyl, naphthyl, pyrenyl, and dansyl chromophores. Their fluorescence behaviors are strongly affected by the dendritic architectures at different generations. These dendrimers modified with hydrophobic chromphores can self-organize into vesicular aggregates at the low generations G0-3 in water. The size and aggregation number of these vesicles decrease with increasing generation from G0 to G3. Critical aggregation concentration determined by fluorescence spectroscopy reveals that these aggregates can be favorably formed in the order of G3 > G2 > G1. In contrast to the vesicles made from traditional amphiphilic compounds, these dendrimer-based vesicles are very adhesive due to the H-bonding interaction and entanglement of dendritic branches located in the outer layer. A large number of multivesicle assemblies, i.e., "twins" and "quins" consisting of two and five vesicles, were clearly identifiable with transmission electron (TEM) and atomic force microscopy. For the dendrimers with peripheral pyrenyl chromophores, triangle-like vesicles were observed in water. The hydrophobic interphase thickness of the vesicular bilayer is ca. 2.0-3.2 nm determined by fluorescence resonance energy transfer methods, which agrees well with the thickness directly observed with TEM.     

The glass transition time scale and configurational entropy in polymers: an experimental molecular view

We report direct experimental observation of local conformational dynamics in a polymer chain at the calorimetric glass transition temperature Tg. Variable-temperature two-dimensional (2D) solid-state exchange NMR, at natural abundance, reveals segmental dynamics in pure polyisobutylene (PIB) occurring on a time scale of several seconds over the Tg range observed by DSC (203-208 K). To our knowledge, this is the first direct observation of molecular-level conformer interchange (trans-trans/trans-gauche/gauche-gauche) at the caloric glass transition temperature. Our results provide a chronologically accurate and pedagogically advantageous demonstration of molecular processes during a polymer phase transition, relative to traditional bulk mechanical and calorimetric techniques. More importantly, we use a miscible blend to demonstrate a general strategy for quantitative evaluation of configurational entropy changes via combination of temperature-dependent 2D exchange NMR and Adams-Gibbs theory. Our results on the Tg time scale are directly relevant to fundamental understanding of the Tg length scale, i.e., the dimension of cooperatively rearranging regions.     

The Synthesis of Some New N‐[1‐(2,5‐Dichlorophenyl)‐5‐Methyl‐1,2,3‐Triazol‐4‐yl]‐Carbamic Acid Ester Derivatives

The synthesis of some new N‐[1‐(2,5‐dichlorophenyl)‐5‐methyl‐1,2,3‐triazol‐4‐yl]‐carbamic acid ester derivatives are reported in this paper. The yielded products 6a‐l were confirmed by Elemental analyses, NMR, MS, and IR spectra.     

两种食用菌菌糠的化学成分分析及热解液化研究

目前,由于煤、石油和天然气等不可再生的化石资源日益枯竭,将可再生的生物质资源转化为能源和化学品受到越来越多的关注[1],其中,热解液化作为独立的热化学转化技术在近年得到了很好的发展[2].     

基于钴离子介导信号转换的抗坏血酸比色分析

抗坏血酸是许多生化过程所必需的一种生物小分子。借助于羟基氧化钴纳米片的氧化性和钴离子与硫氰酸根离子之间强的螯合作用,本文报道了一种基于钴离子介导信号转换的新方法用于抗坏血酸的比色分析。在抗坏血酸存在时,羟基氧化钴纳米片被还原降解产生二价钴离子,钴离子与硫氰酸根离子之间通过螯合作用生成蓝色的阴离子络合物[Co(NCS)₄]^2-,在625nm处产生可见吸收信号。在优化条件下,体系625nm处的吸收值与抗坏血酸浓度在0.03～0.45 mmol/L范围内呈良好的线性关系,线性方程为A₆₂₅=0.638c(mmol/L)+0.042,相关系数R=0.993,检测限(3S/N)为1.5μmol/L。     

计算最小奇异组的一个精化调和Lanczos双对角化方法

在很多实际应用中需要计算大规模矩阵的若干个最小奇异组.调和投影方法是计算内部特征对的常用方法,其原理可用于求解大规模奇异值分解问题.本文证明了,当投影空间足够好时,该方法得到的近似奇异值收敛,但近似奇异向量可能收敛很慢甚至不收敛.根据第二作者近年来提出的精化投影方法的原理,本文提出一种精化的调和Lanczos双对角化方法,证明了它的收敛性.然后将该方法与Sorensen提出的隐式重新启动技术相结合,开发出隐式重新启动的调和Lanczos双对角化算法(IRHLB)和隐式重新启动的精化调和Lanczos双对角化算法(IRRHLB).位移的合理选取是算法成功的关键之一,本文对精化算法提出了一种新的位移策略,称之为"精化调和位移".理论分析表明,精化调和位移比IRHLB中所用的调和位移要好,且可以廉价可靠地计算出来.数值实验表明,IRRHLB比IRHLB要显著优越,而且比目前常用的隐式重新启动的Lanczos双对角化方法(IRLB)和精化算法IRRLB更有效.     

酞菁铁中N4-Fe2+的氧化还原化学和氧还原性能

准确理解金属大环配合物(如N4-Fe2+)体系的氧化还原化学性能,对氧还原反应(ORR)电催化剂的基础研究和合理设计具有重要意义.本文采用微波法将三种不同酞菁铁类金属大环配合物吸附在碳纳米管上,分别记为(NH2)4FePc@CNTs,(t-Bu)4FePc@CNTs和FePc@CNTs,考察了取代基对Fe3+/Fe2+...     

Extraction of Uranium in Nitric Media with Novel Asymmetric Tetra-Alkylcarbamide

The use of tetra-alkylcarbamides as novel ligands: N,N-butyl-N’,N’-hexylurea (L1: ABHU), and N,N-butyl-N’,N’-pentylurea (L2: ABPU), for the solvent extraction and complexation behaviors of uranium(VI) was synthesized and investigated in this study. The effects of HNO₃ and NO₃⁻ concentrations in the aqueous phase on the distribution ratio of U(VI) were examined. Under 5 mol/L HNO₃ concentration, D_U reached 5.02 and 4.94 respectively without third-phase formation. During the extraction, slope measurements and IR spectral analysis revealed that the U(VI) complexes are a form of UO₂(NO₃)₂·2L for both ligands. In addition, thermodynamic studies showed that the uranium extraction reaction was a spontaneous exothermic reaction. The deep structural analysis of the complexes was realized with DFT calculation. The bond length, bond properties, and topology of the complexes were discussed in detail to analyze the extraction behavior. This study enriches the coordination chemistry of U(VI) by tetra-alkylcarbamides, which may offer new clues for the design and synthesis of novel ligands for the separation, enrichment, and recovery of uranium in the nuclear fuel cycle.