Synthesis and Single Crystal Structures of N-Substituted Benzamides and Their Chemoselective Selenation/Reduction Derivatives

A series of N-aryl-N-(2-oxo-2-arylethyl) benzamides and cinnamides has been prepared. The reaction of the benzamides with Woollins’ reagent, a highly efficient chemoselective selenation/reduction reagent, gave the corresponding N-aryl-N-(arylenethyl) benzoselenoamides in good yields. Five representative single crystal X-ray structures are discussed.     

Zn(ferulate)-LSH Systems as Multifunctional Filters

Excessive UV solar radiation exposure causes human health risks; therefore, the study of multifunctional filters is important to skin UV protective ability and also to other beneficial activities to the human organism, such as reduction of reactive oxygen species (ROS) responsible for cellular damages. Potential multifunctional filters were obtained by intercalating of ferulate anions into layered simple metal hydroxides (LSH) through anion exchange and precipitation at constant pH methods. Ultrasound treatment was used in order to investigate the structural changes in LSH-ferulate materials. Structural and spectroscopic analyses show the formation of layered materials composed by a mixture of LSH intercalated with ferulate anions, where carboxylate groups of ferulate species interact with LSH layers. UV-VIS absorption spectra and in vitro SPF measurements indicate that LSH-ferulate systems have UV shielding capacity, mainly UVB protection. The results of reactive species assays show the ability of layered compounds in capture DPPH^•, ABTS^•+, ROO^•, and HOCl/OCl⁻ reactive species. LSH-ferulate materials exhibit antioxidant activity and singular optical properties that enable their use as multifunctional filters.     

Dynamic Visualization of Free Radicals at Single Oxygen Bubbles using Chemiluminescence

The generation of free radicals is a key process in the formation and the collapse of the bubbles in water, however, the direct and dynamic observation of the radicals in this process at single bubbles has never been achieved. Here, the hydroxyl (OH^.) and oxygen (O₂^.−) radicals at single oxygen bubbles are continuously traced using chemiluminescence (CL), in which these radicals at the bubble react with the surrounding luminol in the solution emitting the light. Varied increase trends of luminescence are observed in the generation of a bubble, floating, short parking at the water/air interface and the final explosion, revealing the complexity in the distribution of radicals at the bubble unprecedentedly. Despite more radicals are observed at the bubble generated at a deep position under the water for the stabilization, almost the same amount of radicals are included in the bubbles that is independent on the water pressure during the production of the bubble. This rich information collected from the dynamic study of bubbles illustrates the complicated generation and distribution process of radicals at the bubbles, and will facilitate the understanding of the function about the bubbles.     

最大泡压法测表面张力等温线的数据处理方法比较*

对乙酸、丙酸、正丁酸、2-甲基丁酸、3-甲基丁酸、正戊酸、正己酸、乙醇、丙醇、异丙醇、正丁醇、异丁醇、1,2-丙二醇等13种常用试剂在25 ℃下的表面张力数据拟合方法进行了比较,分析了图解法处理数据及多项式、一阶指数函数、幂函数、Shishkovsky经验公式拟合数据的优缺点。指出Shishkovsky经验公式拟合结果准确,受数据样本量影响小,是理想的表面张力数据拟合方法。     

Analysis of the Magnetic Coupling in a Mn(II)-U(V)-Mn(II) Single Molecule Magnet

[{Mn(TPA)I}{UO2(Mesaldien)}{Mn(TPA)I}]I formula (here TPA=tris(2-pyridylmethyl)amine and Mesaldien=N,N’-(2-aminomethyl)diethylenebis(salicylidene imine)) reported by Mazzanti and coworkers (Chatelain et al. Angew. Chem. Int. Ed. 2014 , 53, 13434) is so far the best Single Molecule Magnet (SMM) in the {3d–5f} class of molecules exhibiting barrier height of magnetization reversal as high as 81.0 K. In this work, we have employed a combination of ab initio CAS and DFT methods to fully characterize this compound and to extract the relevant spin Hamiltonian parameters. We show that the signs of the magnetic coupling and of the g-factors of the monomers are interconnected. The central magnetic unit [U^VO₂]⁺ is described by a Kramers Doublet (KD) with negative g-factors, due to a large orbital contribution. The magnetic coupling for the {Mn(II)-U(V)} pair is modeled by an anisotropic exchange Hamiltonian: all components are ferromagnetic in terms of spin moments, the parallel component J_Z twice larger as the perpendicular one J_⊥. The spin density distribution suggests that spin polarization on the U(V) center favors the ferromagnetic coupling. Further, the J_Z/J_⊥ ratio, which is related to the barrier height, was found to correlate to the corresponding spin contribution of the g-factors of the U(V) center. This correlation established for the first time offers a direct way to estimate this important ratio from the corresponding g^S-values, which can be obtained using traditional ab initio packages and hence has a wider application to other {3d–5f} magnets. It is finally shown that the magnetization barrier height is tuned by the splitting of the [U^VO₂]⁺ 5 f orbitals.     

The Peculiar Dynamics of Cavitation Bubbles

Details from cavitation bubble dynamics are reported: jet formation, counterjet formation, shock wave radiation and light emission. Multiple shock wave radiation from single bubble collapse with jet formation could be time resolved by high speed photography with 20 million frames per second. An explanation of counterjet formation is given. Pictures of the light emission (sonoluminescence) in acoustic cavitation are presented.     

Explosive vaporization in microenclosures

The explosive vaporization of a liquid above planar microheaters induces a fast increase of pressure that is exploited in many thermally driven actuators in MEMS components such as ink jet printer cartridges, pumps, valves and optical switches. Some of these components need to enclose the working fluid as it is the case of valves in which the heated liquid is separated from the flow that it regulates by a flexible membrane. To achieve a better insight into the thermodynamic processes involved, the present work investigates experimentally an enclosed microsystem designed and fabricated for this purpose, composed of a small liquid volume (8 nL) heated by a electric pulse for 2 μs supplied to a planar microfabricated heater. During the heating, the temperature-induced change in resistance can be determined by imposing a defined current and measuring the voltage drop over the heater. While the chip is based on a silicon substrate with integrated platinum heaters and sensors, the structure enclosing the fluid (cavity and fluidic access to it) is made of a silicone elastomer, poly(dimethylsiloxane) (PDMS). This transparent material is widely used in microfluidics and allows for flexible and transparent walls that can be deflected by increasing the pressure inside the cavity. To seal the system the inlet and the outlet were closed by blocking them with a metallic stab. In the present work we visualize vaporization of isopropanol in contact with a suddenly heated planar resistor for two different cavity heights, 150 μm and 16 μm. The rate of temperature rise of the thin liquid layer in contact with the heater is of the order of 10⁷ K s⁻¹ for a pulse duration of 2 μs. We compare bubble growth and collapse for the open and closed systems. Compared to the open system, the bubble growth in the closed system is considerably damped.     

A SINGULAR VALUE DECOMPOSITION BASED TRUNCATION ALGORITHM IN SOLVING THE STRUCTURAL DAMAGE EQUATIONS

The structural damage identification through modal data often leads to solving a set of linear equations. Special numerical treatment is sometimes required for an accurate and stable solution owing to the ill conditioning of the equations. Based on the singular value decomposition (SVD) of the coefficient matrix, an error based truncation algorithm is proposed in this paper. By rejection of selected small singular values, the influence of noise can be reduced. A simply-supported beam is used as a simulation example to compare the results to other methods.Illustrative numerical examples demonstrate the good efficiency and stability of the algorithm in the nondestructive identification of structural damage through modal data.     

Motion of inviscid fluid tongues and bubbles in a Hele-Shaw cell occupied by a viscoelastic fluid

Problems of steady-state motion of an inviscid fluid tongue or bubble in a Hele-Shaw cell occupied by a viscoelastic fluid are considered. The problems generalize the well-known Saffman-Taylor problems [1, 2] in the approximation in which the pressure jump on the interface between the two fluids depends on the normal velocity of the interface [4]. In the zero approximation the results obtained by means of an iteration technique are in good agreement with the analytic solutions obtained by Saffman and Taylor [1, 2].__________Translated from Izvestiya Rossiiskoi Academii Nauk, Mekhanika Zhidkosti i Gaza, No. 1, 2005, pp. 117–123. Original Russian Text Copyright © 2005 by Entov, Kolganov, and Kolganova.     

纤维树脂界面剪切强度及纤维强度分布参数的实验测定

界面剪切强度及纤维强度分布参数是复合材料设计及应用研究中的重要参数，本文采用单纤维段埋入法测定了上述两个参数。通过实验研究说明了单纤维段埋入法是一种测定界面剪切强度及纤维强度分布参数的有效的实验方法；同时证实了基体的力学性能对界面剪切强度有着重要的影响。全部实验在自制的实验系统上完成