The Benzylperoxyl Radical as a Source of Hydroxyl and Phenyl Radicals

The benzyl radical ( 1 ) is a key intermediate in the combustion and tropospheric oxidation of toluene. Because of its relevance, the reaction of 1 with molecular oxygen was investigated by matrix‐isolation IR and EPR spectroscopy as well as computational methods. The primary reaction product of 1 and O₂ is the benzylperoxyl radical ( 2 ), which exists in several conformers that can easily interconvert even at cryogenic temperatures. Photolysis of radical 2 at 365 nm results in a formal [1,3]‐H migration and subsequent cleavage of the O?O bond to produce a hydrogen‐bonded complex between the hydroxyl radical and benzaldehyde ( 4 ). Prolonged photolysis produces the benzoyl radical ( 5 ) and water, which finally yield the phenyl radical ( 7 ), CO, and H₂O. Thus, via a sequence of exothermic reactions 1 is transformed into radicals of even higher reactivity, such as OH and 7 . Our results have implications for the development of models for the highly complicated process of combustion of aromatic compounds.     

Heavy‐Atom Tunneling in the Ring Opening of a Strained Cyclopropene at Very Low Temperatures

The highly strained 1H‐bicyclo[3.1.0]‐hexa‐3,5‐dien‐2‐one 1 is metastable, and rearranges to 4‐oxacyclohexa‐2,5‐dienylidene 2 in inert gas matrices (neon, argon, krypton, xenon, and nitrogen) at temperatures as low as 3 K. The kinetics for this rearrangement show pronounced matrix effects, but in a given matrix, the reaction rate is independent of temperature between 3 and 20 K. This temperature independence means that the activation energy is zero in this temperature range, indicating that the reaction proceeds through quantum mechanical tunneling from the lowest vibrational level of the reactant. At temperatures above 20 K, the rate increases, resulting in curved Arrhenius plots that are also indicative of thermally activated tunneling. These experimental findings are supported by calculations performed at the CASSCF and CASPT2 levels by using the small‐curvature tunneling (SCT) approximation.     

On the Electronic Structure and Photochemistry of Coordinatively Unsaturated Complexes: The Case of Nickel Bis‐dinitrogen,Ni(N2)2

The electronic ground and excited states of the coordinatively unsaturated complex Ni(η¹‐N₂)₂, isolated in an Ar matrix, are analyzed in detail by vibrational and electronic absorption and emission spectroscopies allied with quantum chemical calculations. The bond force constants are determined from a normal coordinate analysis and compared with those of the isoelectronic carbonyl complex. The consequences for the bond properties are discussed, and the trend in the force constants is compared with the standard formation enthalpies. The linear complex Ni(η¹‐N₂)₂ with two terminal dinitrogen ligands can be photoisomerized to two isomeric, metastable forms Ni(η¹‐N₂)(η²‐N₂) and Ni(η²‐N₂)₂, with one and two side‐on coordinated dinitrogen ligands, respectively.     

Alternating Current Electrohydrodynamics Induced Nanoshearing and Fluid Micromixing for Specific Capture of Cancer Cells

We report a new tuneable alternating current (ac) electrohydrodynamics (ac‐EHD) force referred to as “nanoshearing” which involves fluid flow generated within a few nanometers of an electrode surface. This force can be externally tuned via manipulating the applied ac‐EHD field strength. The ability to manipulate ac‐EHD induced forces and concomitant fluid micromixing can enhance fluid transport within the capture domain of the channel (e.g., transport of analytes and hence increase target–sensor interactions). This also provides a new capability to preferentially select strongly bound analytes over nonspecifically bound cells and molecules. To demonstrate the utility and versatility of nanoshearing phenomenon to specifically capture cancer cells, we present proof‐of‐concept data in lysed blood using two microfluidic devices containing a long array of asymmetric planar electrode pairs. Under the optimal experimental conditions, we achieved high capture efficiency (e.g., approximately 90 %; % RSD=2, n=3) with a 10‐fold reduction in nonspecific adsorption of non‐target cells for the detection of whole cells expressing Human Epidermal Growth Factor Receptor 2 (HER2). We believe that our ac‐EHD devices and the use of tuneable nanoshearing phenomenon may find relevance in a wide variety of biological and medical applications.     

Filling a Gap: The Coordinatively Saturated Group 4 Carbonyl Complexes TM(CO)8 (TM=Zr,Hf) and Ti(CO)7

Homoleptic Group 4 metal carbonyl cation and neutral complexes were prepared in the gas phase and/or in solid neon matrix. Infrared spectroscopy studies reveal that both zirconium and hafnium form eight-coordinate carbonyl neutral and cation complexes. In contrast, titanium forms only the six-coordinate Ti(CO)₆⁺ and seven-coordinate Ti(CO)₇. Titanium octacarbonyl Ti(CO)₈ is unstable as a result of steric repulsion between the CO ligands. The 20-electron Zr(CO)₈ and Hf(CO)₈ complexes represent the first experimentally observed homoleptic octacarbonyl neutral complexes of transition metals. The molecules still fulfill the 18-electron rule, because one doubly occupied valence orbital does not mix with any of the metal valence atomic orbitals. Zr(CO)₈ and Hf(CO)₈ are stable against the loss of one CO because the CO ligands encounter less steric repulsion than Zr(CO)₇ and Hf(CO)₇. The heptacarbonyl complexes have shorter metal−CO bonds than that of the octacarbonyl complexes due to stronger electrostatic and covalent bonding, but the significantly smaller repulsive Pauli term makes the octacarbonyl complexes stable.     

A state-of-the-art review on low-frequency nonlinear vibration isolation with electromagnetic mechanisms

Vibration isolation is one of the most efficient approaches to protecting host structures from harmful vibrations, especially in aerospace, mechanical, and architectural engineering, etc. Traditional linear vibration isolation is hard to meet the requirements of the loading capacity and isolation band simultaneously, which limits further engineering application, especially in the low-frequency range. In recent twenty years, the nonlinear vibration isolation technology has been widely investigated to broaden the vibration isolation band by exploiting beneficial nonlinearities. One of the most widely studied objects is the “three-spring” configured quasi-zero-stiffness (QZS) vibration isolator, which can realize the negative stiffness and high-static-low-dynamic stiffness (HSLDS) characteristics. The nonlinear vibration isolation with QZS can overcome the drawbacks of the linear one to achieve a better broadband vibration isolation performance. Due to the characteristics of fast response, strong stroke, nonlinearities, easy control, and low-cost, the nonlinear vibration with electromagnetic mechanisms has attracted attention. In this review, we focus on the basic theory, design methodology, nonlinear damping mechanism, and active control of electromagnetic QZS vibration isolators. Furthermore, we provide perspectives for further studies with electromagnetic devices to realize high-efficiency vibration isolation.

     

光子晶体在提高雷达收发隔离中的应用研究

光子晶体是一种具有频率禁带的新型周期结构,它独特的频率带隙特性使其具有广泛的应用前景.简单介绍了雷达收发隔离常用措施,将光子晶体高阻表面应用到收发隔离中,设计了一种用来改善雷达收发天线隔离度的高阻抗电磁表面结构,实测结果表明该结构改善收发隔离度达15 dB以上,效果显著.     

载频电子散斑位移场分离技术研究

提出了载波调制分离位移场的方法.在双光束电子散斑干涉(ESPI)中增加参考光,使这路参考光为两光束所共用.通过偏转物体引入载波调制条纹,具有条纹对比度高的优点.物体加载后,载波条纹受物体变形的调制而发生弯曲变形.实验时,两束光各自独立地对变形物体进行测量,采集物体变形前后的条纹,利用傅里叶变换法,可分别解调得到包含离面和面内位移信息的2幅位移图.理论分析表明,只需简单的位相运算,就能够将面内位移场与离面位移场分离.利用典型的周边固定、中心加载的圆盘实验,表明了该方法的可行性;周边固定、中心加载的圆盘变形所包含的面内位移大小与离面位移相比,大约低1个数量级.     

New C15 Acetogenins from Two Species of Laurencia from the Aegean Sea

The chemical diversity of the approximately 1,200 natural products isolated from red algae of the genus Laurencia, in combination with the wide range of their biological activities, have placed species of Laurencia in the spotlight of marine chemists’ attention for over 60 years. The chemical investigation of the organic (CH₂Cl₂/MeOH) extracts of Laurencia microcladia and Laurencia obtusa, both collected off the coasts of Tinos island in the Aegean Sea, resulted in the isolation of 32 secondary metabolites, including 23 C₁₅ acetogenins (1–23), 7 sesquiterpenes (24–30) and 2 diterpenes (31 and 32). Among them, six new C₁₅ acetogenins, namely 10-acetyl-sagonenyne (2), cis-sagonenyne (3), trans-thuwalenyne C (4), tinosallene A (11), tinosallene B (12) and obtusallene XI (17), were identified and their structures were elucidated by extensive analysis of their spectroscopic data. Compounds 1–3, 5–11, 13 and 15–32 were evaluated for their antibacterial activity against Staphylococcus aureus and Escherichia coli.     

光学移相干涉仪抗振系统的鲁棒控制系统仿真分析

将被动抗振和主动抗振相结合的混合控制技术应用于解决光学移相干涉仪抗振系统的不确定性问题,其中主动抗振采用鲁棒控制策略.该方法克服了由模型和干扰所引起的不确定性,使得控制系统能够有效地抑制抗振模型的不确定性和外部振动的干扰.仿真结果表明,该方法使光学移相干涉仪在振动的干扰下具有较好的鲁棒稳定性和控制准确度.