Picosecond laser ablation of nickel-based superalloy C263

Picosecond laser (10.4 ps, 1064 nm) ablation of the nickel-based superalloy C263 is investigated at different pulse repetition rates (5, 10, 20, and 50 kHz). The two ablation regimes corresponding to ablation dominated by the optical penetration depth at low fluences and of the electron thermal diffusion length at high fluences are clearly identified from the change of the surface morphology of single pulse ablated craters (dimples) with fluence. The two corresponding thresholds were measured as F _th(D1)¹=0.68±0.02 J/cm² and F _th(D2)¹=2.64±0.27 J/cm² from data of the crater diameters D _1,2 versus peak fluence. The surface morphology of macroscopic areas processed with a scanning laser beam at different fluences is characterised by ripples at low fluences. As the fluence increases, randomly distributed areas among the ripples are formed which appear featureless due to melting and joining of the ripples while at high fluences the whole irradiated surface becomes grainy due to melting, splashing of the melt and subsequent resolidification. The throughput of ablation becomes maximal when machining at high pulse repetition rates and with a relatively low fluence, while at the same time the surface roughness is kept low.     

Study of gas-phase molecular recognition using Fourier transform ion cyclotron resonance mass spectrometry (FTICR/MS)

The application of Fourier transform ion cyclotron resonance (FTICR) mass spectrometry to the quantitative study of molecular recognition in the gas phase is reviewed. Because most quantitative measurements are dependent on accurate determination of the pressure of a neutral reagent, methods for accurate pressure measurement in FTICR, including gauge calibration using a reaction with known rate constants (the traditional method), exothermic proton transfer rate measurement (often the best method when accurate neutral pressures in the trapping cell are desired), and linewidth measurement (a little-used, but generally applicable method) are discussed. The use of rate constant measurements in molecular recognition is illustrated with examples employing natural abundance isotopic labeling to study self-exchange and 2 : 1 ligand:metal complex formation kinetics in crown ether-alkali cation systems. Self-exchange rates do not correlate with alkali cation/crown cavity size relationships, whereas 2 : 1 complex formation kinetics correlate strongly with size relationships. The use of exchange equilibrium constant measurements to characterize molecular recognition is illustrated by alkali cation exchanges between 18-crown-6 and the isomers of dicyclohexano-18-crown-6. These experiments show that the alkyl-substituted ligand binds alkali cations better than unsubstituted 18-crown-6 in the gas phase, in accordance with expectations based on the higher polarizability of the alkyl-substituted ligand. Further, the metal binding thermochemistry differs for the two dicyclohexano-18-crown-6 isomers, with the bowl-shaped cis-syn-cis isomer binding all the alkali cations more strongly than the cis-anti-cis isomer. The measurement of entropies and enthalpies associated with one of the most subtle forms of molecular recognition, enantiomeric discrimination, is illustrated by studies of the discrimination between enantiomers of chiral amines by dimethyldiketopyridino-18-crown-6. This chiral ligand binds chiral primary ammonium cations that have the opposite absolute configuration at their stereocenter more strongly than the enantiomer with the same absolute configuration. Gas-phase studies show that this enantiomeric discrimination is enthalpic in origin, likely related to more favorable pi-pi stacking for the preferred enantiomer. Entropy disfavors binding of the preferred enantiomer.     

飞行光束聚焦特性

一般情况下,Gauss光束基模复参量q的ABCD定律对高阶模是不适用的.将某一特定谐振腔的Rayleigh长度Z_R取代q参量虚部的光斑尺寸w,q参量的ABCD定律可由Gauss光束基模推广到高阶模或几个模的叠加.从理论和实验上研究并比较了当聚焦镜作长距离飞行时理想光学谐振腔和实际高功率激光谐振腔输出的Gauss光束不同模式的远场聚焦特性,纠正了国内外部分学者对这一问题的误解.飞行光束聚焦特性的研究,对于飞行光学激光加工、光学飞行器、大型激光工程空间滤波器等应用领域具有重要研究价值.     

Optical near-field distribution in an asymmetrically illuminated tip–sample system for laser/STM nanopatterning

In surface nano-patterning using an atomic force microscope (AFM) tip in scanning tunnelling microscopy (STM) mode and illuminated by a laser, two controversial physical mechanisms exist in the literature: the field-enhancement (FE) model and the thermal-induced mechanical contact (TMC) model. Due to the presence of evanescent waves in the optical near-field, the exact calculation of the field distribution of the tip–sample system in micro/nano scales becomes complicated. There is a lack of understanding of the asymmetrically illuminated tip–sample system. In this paper, full 3D finite-difference time-domain (FDTD) analysis was carried out to investigate the field distribution in different tip–sample systems. The effects of different tip/sample materials (either dielectric or plasmonic material), the gap distance, and laser incidence angles on the field distribution/enhancement have been studied. For the first time, we have demonstrated two new effects which are helpful in distinguishing the controversial mechanisms: (1) on the sample surface, the field peak position has a shift away from the tip-axis at large angles of incidence, and (2) the field enhancement could depend strongly on the horizontal component (perpendicular to tip-axis) of the incident wave instead of the vertical component (along tip-axis). The optimal incident angle is around 30° for the maximum field under the tip. The existence of field-distribution nodes on the 3D tip surface that leads to the in-homogenous heating of the tip is also predicted. PACS 81.16.Mk; 61.80.Ba; 81.16.Rf; 81.65.Cf     

ALS-associated mutant SOD1<Superscript>G93A</Superscript> causes mitochondrial vacuolation by expansion of the intermembrane space and by involvement of SOD1 aggregation and peroxisomes

Background  

Amyotrophic lateral sclerosis (ALS) is an age-dependent neurodegenerative disease that causes motor neuron degeneration, paralysis and death. Mutations in Cu, Zn superoxide dismutase (SOD1) are one cause for the familial form of this disease. Transgenic mice expressing mutant SOD1 develop age-dependent motor neuron degeneration, skeletal muscle weakness, paralysis and death similar to humans. The mechanism whereby mutant SOD1 induces motor neuron degeneration is not understood but widespread mitochondrial vacuolation has been observed during early phases of motor neuron degeneration. How this vacuolation develops is not clear, but could involve autophagic vacuolation, mitochondrial permeability transition (MPT) or uncharacterized mechanisms. To determine which of these possibilities are true, we examined the vacuolar patterns in detail in transgenic mice expressing mutant SOD1^G93A.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.