Synthesis and optical properties of new chalcones containing 4-[bis(2-hydroxyethyl)amino]phenyl fragment

New chalcones with 4-[bis(2-hydroxyethyl)amino] phenyl fragment were obtained from 4-[bis(2-acetoxyethyl) amino]- benzaldehyde by the Claisen–Schmidt reaction. From their UV-VIS absorption and emission spectra, optical band gap values were calculated based on the Stokes shifts as well as the molar absorption coefficients and fluorescence quantum yields were estimated. The dependence of the absorption and emission maxima on solvent polarity and pH was evaluated.     

Localization and quantification of radical production in cavitating flows with luminol chemiluminescent reactions

Hydrodynamic cavitation experiments in microfluidic systems have been performed with an aqueous solution of luminol as the working fluid. In order to identify where and how much reactive radical species are formed by the violent bubble collapse, the resulting chemiluminescent oxidation reaction of luminol was scrutinized downstream of a constriction in the microchannel. An original method was developed in order to map the intensity of chemiluminescence emitted from the micro-flow, allowing us to localize the region where radicals are produced. Time averaged void fraction measurements performed by laser induced fluorescence experiments were also used to determine the cavitation cloud position. The combination void fraction and chemiluminescence two-dimensional mapping demonstrated that the maximum chemiluminescent intensity area was found just downstream of the cavitation clouds. Furthermore, the radical yield can be obtained with our single photon counting technique. The maximum radical production rates of 1.2*10⁷ OH/s and radical production per processed liquid volume of 2.15*10¹⁰ HO/l were observed. The proposed technique allows for two-dimensional characterisation of radical production in the microfluidic flow and could be a quick, non-intrusive way to optimise hydrodynamic cavitation reactor design and operating parameters, leading to enhancements in wastewater treatments and other process intensifications.     

A simplified green chemistry approach to the Biginelli reaction using ‘Grindstone Chemistry’

Grindstone Chemistry--a greatly evolved version of Toda’s method of grinding solids together for solvent-free chemical reactions--has been described and its usefulness illustrated by the successful application of this technique to a simplified process for conducting the multi-component Biginelli reaction for the synthesis of physiologically active tetrahydropyrimidinones.     

Selective synthesis of dehydroamino acids from threonines

Dehydropeptides containing dehydroamino acid (ΔAA) are frequently found in natural resources with important biological activity. Herein, we report the selective synthesis of Z- and E-ΔAbu from l- and l-allo-threonine as starting materials through selenation and oxidative elimination. The detailed reaction mechanism of phosphine-assisted selenoether formation is also discussed.     

A nucleophilic substitution reaction in microemulsions based on either an alcohol ethoxylate or a sugar surfactant

A nucleophilic substitution reaction between 4-tert-butylbenzyl bromide and a series of iodide salts has been performed in oil-in-water microemulsions based on either a fatty alcohol ethoxylate or a sugar surfactant. The reaction kinetics was compared with the kinetics of the same reaction performed in a microhomogeneous reaction medium, d-MeOH. Previous results showing a particularly high reactivity in the microemulsion based on the fatty alcohol ethoxylate was confirmed. It was shown that in both microemulsions the reaction rate was almost independent of the choice of counterion to iodide. This indicates that complexation of the cation with the surfactant headgroup, which, in particular, could have taken place with surfactants containing oligooxyethylene chains (a “crown ether effect”), seems not to be of importance.

¹²⁷I NMR studies, as well as quadrupole splitting experiments performed by ²H NMR, indicate that there is a certain accumulation of iodide at the oil–water interface of the microemulsions. It is difficult to draw any quantitative conclusions in this respect, however.

The results obtained in this study, combined with results from previous investigations of the same reaction, indicate that the unexpectedly high reactivity obtained in the microemulsion based on a surfactant containing an oligooxyethylene headgroup is most probably due to the nucleophile being poorly solvated when present in the headgroup layer of such a microemulsion. Poorly solvated anions are known to be highly reactive nucleophiles.     

Control Policy for a Manufacturing System with Random Yield and Rework

We develop a production policy that controls work-in-process (WIP) levels and satisfies demand in a multistage manufacturing system with significant uncertainty in yield, rework, and demand. The problem addressed in this paper is more general than those in the literature in three aspects: (i) multiple products are processed at multiple workstations, and the capacity of each workstation is limited and shared by multiple operations; (ii) the behavior of a production policy is investigated over an infinite-time horizon, and thus the system stability can be evaluated; (iii) the representation of yield and rework uncertainty is generalized. Generalizing both the system structure and the nature of uncertainty requires a new mathematical development in the theory of infinite-horizon stochastic dynamic programming. The theoretical contributions of this paper are the existence proofs of the optimal stationary control for a stochastic dynamic programming problem and the finite covariances of WIP and production levels under the general expression of uncertainty. We develop a simple and explicit sufficient condition that guarantees the existence of both the optimal stationary control and the system stability. We describe how a production policy can be constructed for the manufacturing system based on the propositions derived.     

正电子产生靶上初级电子束半径的最小化研究

为获得尽可能高的正电子(e⁺)产额,严格控制初级电子(e^－)束在e⁺产生靶上的束半径是至关重要的.首先分析了使e^－束半径增大的各因素和对这些因素的制约;然后以北京正负电子对撞机(BEPC)的正电子源为例,给出了束半径的实测值和计算值的比较,以具体说明这些因素的影响;最后讨论了北京正负电子对撞机二期工程(BEPC-Ⅱ)的相应优化设计研究,提出了获得靶上最小束半径的若干途径.     

新型噻吩基取代卟啉的合成及其荧光光谱研究

合成了两种新型噻吩基卟啉－5，15－二（2－噻吩基）－2，8，12，18－四乙基－3，7，13，17－四甲基卟啉7a（45．1％）和5，15－二（2－联噻吩基）－2，8，12，18－四乙基－3，7，13，17－四甲基卟啉7b(61.2%),并研究了它们的光谱性质，其中荧光光谱的最大发射峰蜂都在631nm处，量子产率分别为4．1％（7a)和1．4％（7b)。     

Crystal dissolution kinetics and Gibbs free energy

The dependence of dissolution rates on the difference of Gibbs free energy is of critical importance for our understanding of crystal dissolution, reactive flow models and their applications to a variety of environmentally related problems. Here, we review experimental data generated with mineral powders and single crystals to develop a better understanding of apparent inconsistencies between otherwise internally consistent data sets. Additional information from direct surface observations and measurements with vertical scanning interferometry (VSI) and atomic force microscopy (AFM) of albite dissolution at 25, 150 and 185 °C may shed new light on this old but unsolved question. Our discussion is based on the importance of etch pit development, its ΔG dependence, and the pits’ role as a source for steps and step movement in the dissolution process. Results indicate that reaction history may be of critical importance in determining the overall reaction mechanism and its rate. Different rates are observed for systems having otherwise identical ΔG_r acquired from increasing versus decreasing disequilibrium positions.

In this context, we finally discuss the validity of the common application of transition state theory (TST) to elementary and overall reactions governing the dissolution process. In this discussion of crystal dissolution, we contrast TST applications with a stochastic, many-body treatment that has led to the development of a stepwave model. This discussion also focuses on the controversy caused by the rivalry between surface adsorption models and a probabilistic model that seeks to incorporate the full three-dimensional crystal structure.     

影响DPF焦点装置中子稳定性的因素和改进措施

简要叙述了稠密等离子体聚焦装置作为中子发生器的工作原理，对影响稠密等离子体聚焦装置放电出中子产额及其稳定性的一些因素和改进措施进行了简单讨论．通过使用不同电极形状的场畸变开关很好地提高了焦点装置的运行，使装置输出中子的起伏得到明显的改善．通过对腔内电极的清洁，在不更换气体的条件下，聚焦装置放电出中子产额稳定.The principle of dense plasma focus(DPF) as neutron generator has been investigated in this paper. We have stated briefly some factors that mainly influnce the DPF s neutron yield and some methods improving the stability of neutron yields on the dense plasma focus. It is showed that the fluctuation of DPF output neutron becomes smaller by using different types of field-distortion elements. Over 100 consecutive shots without purging the test gas the neutron yields has no obvious change.