Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C1 and C18 ligands of different densities

Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C₁ and C₁₈ alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D_s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C₁ and C₁₈ ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D_s values under various RPLC conditions. The D_s values can be estimated with a mean square deviation of about 25–30%. The agreement between the D_s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C₁ and C₁₈ ligands and that the contribution of each ligand is proportional to the ligand density.     

Theoretical Study on the Dark Oxidation Reaction Mechanism of Ethers

1 INTRODUCTION Ethers are a kind of organic compounds that are easily oxidized under the conditions of lacking light and any additional excitement. According to dif- ferent mechanisms, the oxidation reactions could be classified into two types: photooxidation reaction and dark oxidation reaction. The former is the reaction with excited state oxygen molecule (singlet state), while the latter is the reaction with ground state oxygen molecule (triple state) without illuminance or any exciter…     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.     

Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.     

负载扰动观测器在SF型矢量控制系统中的应用

文章提出广义逆矩阵来设计离散型状态观测器的方法,用该法设计的观测器,可对SF型矢量控制系统的负载力矩进行估计,再进行前馈补偿。实验证明,该法可有效改善系统的动态性能。     

利用8098单片机的热电偶参比端温度的全补偿方法

本文介绍在采用微机来进行热电偶测温处理时,通过查表的方法实现参比端温度的完全补偿,并完成热电势到温度的处理。     

一种磁滞可调110/220 V自动切换系统

开发了１１０／２２０Ｖ电网自动切换系统,采用设置延迟时间和磁滞回线的方法,有效地防止了启动时误动作,避免在切换点附近频繁切换动作,讨论了延迟时间及磁滞回线回路的计算方法。     

利用虚拟目标值的预见控制设计(英文)

研究了预见跟踪控制问题,即控制器可利用过去、现在和未来的信息来决定所施加控制量的大小．通常的作法是通过把未来预见信息加入控制量中来实现的．提出了一种不同的作法：利用未来目标值及系统的当前状态产生一个虚拟目标值,让系统转而去跟踪这个已被事先处理过的目标值信号,从而提高了系统的控制精度同时减少了控制所需的能量．数值仿真表明了这种方法的优越性．