Dibenzyl trithiocarbonate mediated reversible addition-fragmentation chain transfer polymerization of acrylonitrile

Reversible addition-fragmentation chain transfer polymerization has been successfully applied to polymerize acrylonitrile with dibenzyl trithiocarbonate as the chain-transfer agent. The key to success is ascribed to the improvement of the interchange frequency between dormant and active species through the reduction of the activation energy for the fragmentation of the intermediate. The influence of several experimental parameters, such as the molar ratio of the chain-transfer agent to the initiator [azobis(isobutyronitrile)], the molar ratio of the monomer to the chain-transfer agent, and the monomer concentration, on the polymerization kinetics and the molecular weight as well as the polydispersity has been investigated in detail. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 NMR analyses have confirmed the chain-end functionality of the resultant polymer.

Effects of SBS addition and temperature on 3D siliceous mesostructured cellular foam

Siliceous mesostructured cellular foam with three-dimensional (3D) wormhole structure (MSU-type) is prepared by using triblock copolymer (poly(styrene-b-butadiene-b- styrene), SBS) with both hydrophobic head and tail group as template in strong acid condition via microemulsion method. The effects of SBS addition and temperature on the morphology and physicochemical properties, such as pore diameters, surface areas and pore volumes of the materials have been investigated by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscope (FE-SEM) and nitrogen adsorption-desorption analysis. The results show that the pore volumes, pore sizes and specific surface areas depend strongly on the SBS amount and forming micelles temperature. Moreover, the materials obtained with high wall thickness exhibit a relatively good thermal stability.

Gas Phase Addition of Rare-earth Fullerenes with Benzene

Gas phase adduct of endohedral rare-earth fullerenes Nd@C-S2 with the ion system of benzene-[Nd@C-S2-C6H6](+) was observed for the first time by ion-molecular reaction under chemical ionization condition. The possible reaction passageway and molecular structures of this gas phase adduct were discussed and a parallel "reversed umbrella" pi-pi interaction complex of the [C6H6](+) ion reacting with the neutral rare-earth fullerenes Nd@C-S2 was considered to be much reasonable. The experimental result indicated that endohedral rare-earth fullerenes has relatively active reactivity and aromatic properties similar towards benzene molecular ion in gas phase.

A unified criterion for initiation of sediment motion and inception of sheet flow under water waves

A unified criterion is developed for initiation of non-cohesive sediment motion and inception of sheet flow under water waves over a horizontal bed of sediment based on presently available experimental data. The unified threshold criterion is of the single form, U-o = 2 pi C[1 + 5(T-R/T)(2)](-1/4), where U-o is the onset velocity of sediment motion or sheet flow, T is wave period, and C and T-R are the coefficients. It is found that for a given sediment, U-o initially increases sharply with wave period, then gradually approaches the maximum onset velocity U-o = 2 pi C and becomes independent of T when T is larger. The unified criterion can also be extended to define sediment initial motion and sheet flow under irregular waves provided the significant wave orbital velocity and period of irregular waves are introduced in this unified criterion.

Addition reactions of nitrones on the reconstructed C(100)-2 x 1 surfaces

In this paper, the reactions of nitrone, N-methyl nitrone, N-phenyl nitrone and their hydroxylamine tautomers (vinyl-hydroxylamine, N-methyl-vinyl-hydroxylamine and N-phenyl-vinyl-hydroxylamine) on the reconstructed C(100)-2 x 1 surface have been investigated using hybrid density functional theory (B3LYP), Moller-Plesset second-order perturbation (MP2) and multi-configuration complete-active-space self-consistent-field (CASSCF) methods. The calculations showed that all the nitrones can react with the surface "dimer" via facile 1.3-dipolar cycloaddition with small activation barriers (less than 12.0 kJ/mol at B3LYP/6-31g(d) level). The [2+2] cycloaddition of hydroxylamine tautomers on the C(100) surface follows a diradical mechanism. Hydroxylamine tautomers first form diradical intermediates with the reconstructed C(I 00)-2 x I surface by overcoming a large activation barrier of 50-60 kJ/mol (B3LYP), then generate [2+2] cycloaddition products via diradical transition states with negligible activation barriers. The surface reactions result in hydroxyl or amino-terminated diamond surfaces, which offers new opportunity for further modifications. (C) 2007 Elsevier B.V. All rights reserved.

Addition reaction of nitrones on the reconstructed Si(100)-2 x 1 surface

The reaction of nitrone, N-methyl nitrone, and their hydroxylamine tautomers (vinyl-hydroxylamine and N-methyl vinyl-hydroxylamine) on the reconstructed Si(100)-2 x 1 surface has been investigated by means of hybrid density functional theory (B3LYP) and Moller-Plesset second-order perturbation (MP2) methods. The calculations predicted that both of the nitrones should react with the surface dimer via facile concerted 1,3-dipolar cycloaddition leading to 5-member-ring compounds. The reaction of hydroxylamine tautomers on the Si(100) surface follows pi-complex (intermediate) mechanism. For the reaction of N-methyl vinyl-hydroxylamine, the pi-complex intermediate undergoes [2+2] cycloaddition leading to a 4-member-ring compound. But in the reaction of vinyl-hydroxylamine, the intermediate undergoes H-migration reaction ("ene" reaction) resulting in the oxime-terminated Si surface. All the surface reactions result in the hydroxyl-terminated silicon surfaces, which are very useful for the further modification of the semiconductor.

Theoretical study on the mechanism for the addition reaction of SiH3 with propylene and acetic acid

To explore the reactivities of alkene (-CH=CH2) and carboxy (-COOH) group with H-Si under UV irradiation, the addition mechanism for the reactions of SiH3 radical with propylene and acetic acid was studied by using the B3LYP/6-311++ G(d,p) method. Based on the surface energy profiles, the dominant reaction pathways can be established; i.e., SiH3 adds to the terminal carbon atom of the alkene (-CH=CH2) to form an anti-Markovnikov addition product, or adds to the oxygen atom of the carboxy group (-COOH) to form silyl acetate (CH3-COOSiH3). Because the barrier in the reaction of the carboxy group (39.9 kJ/ mol) is much larger than that of alkene (11.97 kJ/mol), we conclude that the reaction of bifunctional molecules (e.g., omega-alkenoic acid) with H-Si under irradiation condition is highly selective; i.e., the alkene group (-CH= CH2) reacts with SiH3 substantially faster than the carboxyl group (-COOH), which agrees well with the experimental results. This provides the possibility of preparing carboxy-terminated monolayers on silicon surface from omega-alkenoic acids via direct photochemical reaction.

Elliptic Object Detection Based on Shape Preserving and Active Contour

本文通过形状约束方程(组)与一般主动轮廓模型结合,将目标形状与主动轮廓模型融合到统一能量泛函模型中,提出了一种形状保持主动轮廓模型即曲线在演化过程中保持为某一类特定形状。模型通过参数化水平集函数的零水平集控制演化曲线形状,不仅达到了分割即目标的目的,而且能够给出特定目标的定量描述。根据形状保持主动轮廓模型,建立了一个用于椭圆状目标检测的统一能量泛函模型,导出了相应的Euler-Lagrange常微分方程并用水平集方法实现了椭圆状目标检测。此模型可以应用于眼底乳头分割,虹膜检测及相机标定。实验结果表明,此模型不仅能够准确的检测出给定图像中的椭圆状目标,而且有很强的抗噪、抗变形及遮挡性能。

基于形状保持主动轮廓模型长直条的检测

通过形状约束方程(组)与一般主动轮廓模型结合,将目标形状与主动轮廓模型融合到统一能量泛函模型中,提出一种形状保持主动轮廓模型。模型通过参数化水平集函数的零水平集表示某一类特定形状,不仅达到了分割即目标的目的,而且能够给出特定目标的定量描述。根据形状保持主动轮廓模型,建立一个用于长直条状目标检测的统一能量泛函模型,导出相应的Euler-Lagrange常微分方程并用水平集方法实现了长直条状区域的检测。此形状保持模型的一种特殊情况可以用于直线状地平(海天)线提取。实验结果表明,该模型不仅能够准确地检测出给定图像中的长直条状区域而且有很强的抗噪、抗变形及遮挡性能。

大型反倾岩体变形破坏机制及稳定性分析———以金沙江宽谷坝址龙蟠边坡为例

A large number of catastrophic accidents were aroused by the instability and destruction of anti-dip rock masses in the worldwide engineering projects, such as hydropower station, mine, railways and so on. Problems in relation to deformation and failure about anti-dip rock slopes are significant for engineering geology research. This dissertation takes the Longpan slope in the Jinsha River as a case to study the deformation mechanism of large-scale anti-dip rock masses and the slope stability analysis method. The primary conclusions are as follows. The Dale Reach of Jinsha River, from Longpan to the debouchment of Chongjiang tributary, is located in the southeastern margin of the Qinghai-Tibet Plateau. Longpan slope is the right embankment of Dale dam, it is only 26 km to the Shigu and 18 km to Tiger Leaping Gorge. The areal geology tectonic structures here area are complicated and blurry. Base on the information of geophysical exploration (CSAMT and seismology) and engineering geological investigation, the perdue tectonic pattern of Dale Reach is put forward for the first time in this paper. Due to the reverse slip of Longpan fault and normal left-rotation of Baihanchang fault, the old faulted valley came into being. The thick riverbed sediments have layered characters of different components and corresponding causes, which attribute to the sedimentary environments according with the new tectonic movements such as periodic mountain uplifting in middle Pleistocene. Longpan slope consists of anti-dip alternate sandstone and slate stratums, and the deformable volume is 6.5×107m3 approximately. It was taken for an ancient landslide or toppling failure in the past so that Dale dam became a vexed question. Through the latest field surveying, displacement monitoring and rock masses deforming characters analyses, the geological mechanism is actually a deep-seated gravitational bending deformation. And then the discrete element method is used to simulate the deforming evolution process, the conclusion accords very well with the geo-mechanical patterns analyses. In addition strength reduction method based on DEM is introduced to evaluate the factor of safety of anti-dip rock slope, and in accordance with the expansion way of the shear yielding zones, the progressive shear failure mechanism of large-scale anti-dip rock masses is proposed for the first time. As an embankment or a close reservoir bank to the lower dam, the stability of Longpan slope especially whether or not resulting in sliding with high velocity and activating water waves is a key question for engineering design. In fact it is difficult to decide the unified slip surface of anti-dip rock slope for traditional methods. The author takes the shear yielding zones acquired form the discrete element strength reduction calculation as the potential sliding surface and then evaluates the change of excess pore pressure and factor of stability of the slope generated by rapid drawdown of ponded water. At the same time the dynamic response of the slope under seismic loading is simulated through DEM numerical modeling, the following results are obtained. Firstly the effective effect of seismic inertia force is resulting in accumulation of shear stresses. Secondly the discontinuous structures are crucial to wave transmission. Thirdly the ultimate dynamic response of slope system takes place at the initial period of seismic loading. Lastly but essentially the effect of earthquake load to bringing on deformation and failure of rock slope is the coupling effect of shear stresses and excess pore water pressure accumulation. In view of limitations in searching the critical slip surface of rock slope of the existing domestic and international software for limit equilibrium slope stability analyses, this article proposes a new method named GA-Sarma Algorithm for rock slope stability analyses. Just as its name implies, GA-Sarma Algorithm bases on Genetic Algorithm and Sarma method. GA-Sarma Algorithm assumes the morphology of slip surface to be a broken line with traceability to extend along the discontinuous surface structures, and the slice boundaries is consistent with rock mass discontinuities such as rock layers, faults, cracks, and so on. GA-Sarma Algorithm is revolutionary method that is suitable for global optimization of the critical slip surface for rock slopes. The topics and contents including in this dissertation are closely related to the difficulties in practice, the main conclusions have been authorized by the engineering design institute. The research work is very meaningful and useful for the engineering construction of Longpan hydropower station.

Removal of NO by microwave discharge with the addition of CH4

Removal of NO by a continuous microwave discharge at atmospheric pressure with the addition of CH4 is reported. The conversion of NO to N-2 is approximately 80%, and the energy efficiency is up to 0.55 g-NO/kWh. The effects of CH4 addition and three discharge modes on NO conversion and energy efficiency are investigated. The dependence of NO conversion on experimental time is also observed.