Applying Unconventional Spectroscopies to the Single-Molecule Magnets,Co(PPh3)2X2 (X=Cl,Br, I): Unveiling Magnetic Transitions and Spin-Phonon Coupling

Large separation of magnetic levels and slow relaxation in metal complexes are desirable properties of single-molecule magnets (SMMs). Spin-phonon coupling (interactions of magnetic levels with phonons) is ubiquitous, leading to magnetic relaxation and loss of memory in SMMs and quantum coherence in qubits. Direct observation of magnetic transitions and spin-phonon coupling in molecules is challenging. We have found that far-IR magnetic spectra (FIRMS) of Co(PPh₃)₂X₂ ( Co-X ; X=Cl, Br, I) reveal rarely observed spin-phonon coupling as avoided crossings between magnetic and u-symmetry phonon transitions. Inelastic neutron scattering (INS) gives phonon spectra. Calculations using VASP and phonopy programs gave phonon symmetries and movies. Magnetic transitions among zero-field split (ZFS) levels of the S=3/2 electronic ground state were probed by INS, high-frequency and -field EPR (HFEPR), FIRMS, and frequency-domain FT terahertz EPR (FD-FT THz-EPR), giving magnetic excitation spectra and determining ZFS parameters (D, E) and g values. Ligand-field theory (LFT) was used to analyze earlier electronic absorption spectra and give calculated ZFS parameters matching those from the experiments. DFT calculations also gave spin densities in Co-X , showing that the larger Co(II) spin density in a molecule, the larger its ZFS magnitude. The current work reveals dynamics of magnetic and phonon excitations in SMMs. Studies of such couplings in the future would help to understand how spin-phonon coupling may lead to magnetic relaxation and develop guidance to control such coupling.     

Vernodalidimers A and B, novel orthoester elemanolide dimers from seeds of Vernonia anthelmintica

Two novel elemanolide dimers, vernodalidimers A (1) and B (2), possessing a rare tricyclic ortho ester moiety, were isolated from the seeds of Vernonia anthelmintica. Their structures were elucidated by 1D and 2D NMR data and CD spectra. Vernodalidimers A (1) and B (2) exhibited potent cell growth inhibitory activity against HL-60 cells (IC₅₀ 0.72 and 0.47 μM, respectively).     

LabVIEW与Matlab在信息光学教学中的应用

计算机仿真技术已经被广泛应用到教学和科研中.将LabVIEW和Matlab引入信息光学课程教学中,通过设计相关的程序,可使复杂的物理理论以形象直观的实验仿真表现出来.经过实践证明,该措施可提高学生的学习兴趣和教学质量.     

Coulomb forces on DNA polymers in charged fluidic nanoslits

We investigate the repulsive electrostatic interactions between a DNA polyelectrolyte and the charged walls of a fluidic nanoslit. The scaling of the DNA coil size with the physical slit height revealed electrostatic depletion regions that reduced the effective slit height. These regions exceeded the Debye screening length of the buffer, λ(D)(buffer), and saturated at ≈ 50 nm when λ(D)(buffer) reached 10 nm. We explain these results by modeling a semiflexible charged rod near a charged wall and the electrostatic screening by the polyelectrolyte. These results demonstrate the surprisingly long range over which a nanofluidic device can exert field-effect control over confined molecules.     

激光辐照环境对金属材料反射特性的影响

 利用积分球绝对测量法,对在20 Pa真空缺氧、1 000 Pa空气,10⁵ Pa空气及1 000 Pa氧气环境下,1 064 nm波长连续激光辐照30CrMnSiA碳钢材料过程中的反射光信号进行了测量,得到了30CrMnSiA碳钢在4种辐照环境下的反射率和温度变化曲线。结果表明：在空气组分辐照环境的低压到10⁵ Pa范围内,材料初始反射率随压力增大而增大;在缺氧和富氧环境的激光辐照过程中,缺氧环境下材料反射率变化缓慢,且变化拐点温度高于富氧环境,富氧环境下材料被加热后的快速氧化反应有利于材料对激光能量的吸收;不同辐照环境（缺氧和富氧）相同材料温度条件下,材料反射率并不相同。     

全密度功能性复杂金属零件的激光直接快速制造

 针对具有复杂结构的全密度功能性金属零件快速制造难题,探讨了该类零件的选区激光熔化直接快速制造方法,并结合实验,重点对同步保证选区激光熔化快速制造金属零件成型密度及精度的工艺进行了研究。结果表明：同步消除球化、飞溅及气孔对成型件致密性及精度的影响是实现选区激光熔化快速制造全密度功能性复杂金属零件的难点及关键;在维持良好的抗氧化气氛条件下,可采用尽可能薄的铺粉厚度及恰当调节其它成型参数的方法,以保证对上一层有足够的重熔量来消除球化及气孔现象;同时,采用合适的扫描策略,可弱化飞溅对成型质量的影响来解决工艺难题。采用该工艺方案可快速制造全密度功能性复杂金属零件,所成型的316L不锈钢叶轮零件相对密度为99.8%,硬度为HB192,表面粗糙度约为40 μm,尺寸精度在±0.1 mm以内,稍经打磨后即可投入使用。     

Effects of pulsed bias duty ratio on microstructure and mechanical properties of TiN/TiAlN multilayer coatings

TiN/TiAlN multilayer coatings were deposited on M2 high speed steel by a pulsed bias arc ion plating system. The effect of pulsed bias duty ratio on the microstructure, mechanical and wear properties was investigated. The amount of macroparticles reduced with the increase of the duty ratio. The surface roughness was 0.0858 μm at duty ratio of 50%. TiN/TiAlN multilayer coatings were crystallized with orientations in the (1 1 1), (2 0 0) (2 2 2) and (3 1 1) crystallographic planes and the microstructure strengthened at (1 1 1) preferred orientation. At duty ratio of 20%, the hardness of TiN/TiAlN multilayer coatings reached a maximum of 3004 HV, which was 3.2 times that of the substrate. The adhesion strength reached a maximum of 77 N at 50% duty ratio. Friction and wear analyses were carried out by pin-on-disc tester at room temperature. Compared with the substrate, all the specimens coated with TiN/TiAlN multilayer coatings exhibited better tribological properties.     

Constructing differentially 4-uniform permutations over GF(22m ) from quadratic APN permutations over GF(22m+1)

In this paper, by means of the idea proposed by Carlet (ACISP 1-15, 2011), differentially 4-uniform permutations with the best known nonlinearity over \({\mathbb{F}_{2^{2m}}}\) are constructed using quadratic APN permutations over \({\mathbb{F}_{2^{2m+1}}}\) . Special constructions are given using the Gold functions. The algebraic degree of the constructions and their compositional inverses is also investigated. One construction and its compositional inverse both have algebraic degree m + 1 over \({\mathbb{F}_2^{2m}}\) .     

A matrix approach for constructing quadratic APN functions

A one to one correspondence is given between quadratic homogeneous APN functions and a special kind of matrices which we call as QAM’s. By modifying the elements of a known QAM, new quadratic APN functions can be constructed. Based on the nice mathematical structures of the QAM’s, an efficient algorithm for constructing quadratic APN functions is proposed. On \(\mathbb {F}_{2^7}\) , we have found 471 new CCZ-inequivalent quadratic APN functions, which is 20 times more than the number of the previously known ones. Before this paper, It is only found 23 classes of CCZ-inequivalent APN functions on \(\mathbb {F}_{2^8}\) . With the method of this paper, we have found 2,252 new CCZ-inequivalent quadratic APN functions, and this number is still increasing.     

Characterizing fracture energy of proton exchange membranes using a knife slit test

Pinhole formation in proton exchange membranes (PEM) may be caused by a process of flaw formation and crack propagation within membranes exposed to cyclic hygrothermal loading. Fracture mechanics can be used to characterize the propagation process, which is thought to occur in a slow, time‐dependent manner under cyclic loading conditions, and believed to be associated with limited plasticity. The intrinsic fracture energy has been used to characterize the fracture resistance of polymeric material with limited viscoelastic and plastic dissipation, and has been found to be associated with long‐term durability of polymeric materials. Insight into this limiting value of fracture energy may be useful in characterizing the durability of proton exchange membranes, including the formation of pinhole defects. In an effort to collect fracture data with limited plasticity, a knife slit test was adapted to measure fracture energies of PEMs, resulting in fracture energies that were two orders of magnitude smaller than those obtained with other fracture test methods. The presence of a sharp knife blade reduces crack tip plasticity, providing fracture energies that may be more representative of the intrinsic fracture energies of the thin membranes. Three commercial PEMs were tested to evaluate their fracture energies (G_c) at temperatures ranging from 40 to 90 °C and humidity levels varying from dry to 90% relative humidity (RH). Experiments were also conducted with membrane specimens immersed in water at various temperatures. The time temperature moisture superposition principle was applied to generate fracture energy master curves plotted as a function of reduced cutting rate based on the humidity and temperature conditions of the tests. The shift with respect to temperature and humidity suggests that the slitting process is viscoelastic in nature. Also such shifts were found to be consistent with those obtained from constitutive tests such as stress relaxation. The fracture energy is more sensitive to temperature than on humidity. The master curves converge at the lowest reduced cutting rates, suggesting similar intrinsic fracture energies; but diverge at higher reduced cutting rates to significantly different fracture energies. Although the relationship between G_c and ultimate mechanical durability has not been established, the test method may hold promise for investigating and comparing membrane resistance to failure in fuel cell environments. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 333–343, 2010