Yuan-Tseh Lee

Infrared spectrum of NH4+(H2O): Evidence for mode specific fragmentation

The gas phase infrared spectrum (3250-3810 cm-1) of the singly hydrated ammonium ion, NH4+(H2O), has been recorded by action spectroscopy of mass selected and isolated ions. The four bands obtained are assigned to N-H stretching modes and to O-H stretching modes. The N-H stretching modes observed are blueshifted with respect to the corresponding modes of the free NH4+ ion, whereas a redshift is observed with respect to the modes of the free NH3 molecule. The O-H stretching modes observed are redshifted when compared to the free H2O molecule. The asymmetric stretching modes give rise to rotationally resolved perpendicular transitions. The K-type equidistant rotational spacings of 11.1(2) cm-1 (NH4+) and 29(3) cm-1 (H2O) deviate systematically from the corresponding values of the free molecules, a fact which is rationalized in terms of a symmetric top analysis. The relative band intensities recorded compare favorably with predictions of high level ab initio calculations, except on the nu3(H2O) band for which the observed value is about 20 times weaker than the calculated one. The nu3(H2O)/nu1(H2O) intensity ratios from other published action spectra in other cationic complexes vary such that the nu3(H2O) intensities become smaller the stronger the complexes are bound. The recorded ratios vary, in particular, among the data collected from action spectra that were recorded with and without rare gas tagging. The calculated anharmonic coupling constants in NH4+(H2O) further suggest that the coupling of the nu3(H2O) and nu1(H2O) modes to other cluster modes indeed varies by orders of magnitude. These findings together render a picture of a mode specific fragmentation dynamic that modulates band intensities in action spectra with respect to absorption spectra. Additional high level electronic structure calculations at the coupled-cluster singles and doubles with a perturbative treatment of triple excitations [CCSD(T)] level of theory with large basis sets allow for the determination of an accurate binding energy and enthalpy of the NH4+(H2O) cluster. The authors extrapolated values at the CCSD(T) complete basis set limit are De [NH4+-(H2O)]=-85.40(+/-0.24) kJ/mol and DeltaH(298 K) [NH4+-(H2O)]=-78.3(+/-0.3) kJ/mol (CC2), in which double standard deviations are indicated in parentheses.

A study on the buckling behavior of an orthotropic square plate with a central circular hole

Abstract The buckling behavior of orthotropic square plate, either with or without a central circular hole, is analyzed with the aid of the finite element method. Materials with different degrees of orthotropy are examined. Both uniaxial and biaxial compression are considered for various boundary conditions. For highly orthotropic material under uniaxial or biaxial compression in the weaker direction, there is a tendency for the lowest buckling mode not to be a single half-wave. It is found that the first buckling mode may be two or three half-waves, depending on the degrees of orthotropy as well as boundary conditions. The characteristics of buckling strength and mode shape of orthotropic plates with central circular holes are presented and discussed in this paper.

Thermal Proton Transfer Reactions in Ultraviolet Matrix-Assisted Laser Desorption/Ionization

AbstractOne of the reasons that thermally induced reactions are not considered a crucial mechanism in ultraviolet matrix-assisted laser desorption ionization (UV-MALDI) is the low ion-to-neutral ratios. Large ion-to-neutral ratios (10–4) have been used to justify the unimportance of thermally induced reactions in UV-MALDI. Recent experimental measurements have shown that the upper limit of the total ion-to-neutral ratio is approximately 10–7 at a high laser fluence and less than 10–7 at a low laser fluence. Therefore, reexamining the possible contributions of thermally induced reactions in MALDI may be worthwhile. In this study, the concept of polar fluid was employed to explain the generation of primary ions in MALDI. A simple model, namely thermal proton transfer, was used to estimate the ion-to-neutral ratios in MALDI. We demonstrated that the theoretical calculations of ion-to-neutral ratios exhibit the same trend and similar orders of magnitude compared with those of experimental measurements. Although thermal proton transfer may not generate all of the ions observed in MALDI, the calculations demonstrated that thermally induced reactions play a crucial role in UV-MALDI.n Figureᅟ

Ionization Mechanism of Matrix-Assisted Laser Desorption/Ionization

In past studies, mistakes in determining the ionization mechanism in matrix-assisted laser desorption/ionization (MALDI) were made because an inappropriate ion-to-neutral ratio was used. The ion-to-neutral ratio of the analyte differs substantially from that of the matrix in MALDI. However, these ratios were not carefully distinguished in previous studies. We begin by describing the properties of ion-to-neutral ratios and reviews early experimental measurements. A discussion of the errors committed in previous theoretical studies and a comparison of recent experimental measurements follow. We then describe a thermal proton transfer model and demonstrate how the model appropriately describes ion-to-neutral ratios and the total ion intensity. Arguments raised to challenge thermal ionization are then discussed. We demonstrate how none of the arguments are valid before concluding that thermal proton transfer must play a crucial role in the ionization process of MALDI.

Strength of composite laminates with continuous fiber around a circular hole

Abstract The strength of glass fiber woven roving composites containing a circular hole was examined. Two types of circular hole — drilled, and moulded-in — were considered. Experiments were conducted on four different sizes of hole diameter. Experimental results show that specimens with a moulded-in circular hole exhibit failure at a higher strength than those with a drilled hole and exhibit different failure mode. A strength enhancement of 28–77% as compared with drilled laminates was observed. In addition to explaining the experimental results, a simple finite element model which used the concept of the stream line to simulate the fiber configuration was used in the stress analysis of laminates with moulded-in circular holes. The numerical results may explain why the laminates with moulded-in holes are stronger than those with drilled holes.

Ion-to-Neutral Ratios and Thermal Proton Transfer in Matrix-Assisted Laser Desorption/Ionization

AbstractThe ion-to-neutral ratios of four commonly used solid matrices, α-cyano-4-hydroxycinnamic acid (CHCA), 2,5-dihydroxybenzoic acid (2,5-DHB), sinapinic acid (SA), and ferulic acid (FA) in matrix-assisted laser desorption/ionization (MALDI) at 355 nm are reported. Ions are measured using a time-of-flight mass spectrometer combined with a time-sliced ion imaging detector. Neutrals are measured using a rotatable quadrupole mass spectrometer. The ion-to-neutral ratios of CHCA are three orders of magnitude larger than those of the other matrices at the same laser fluence. The ion-to-neutral ratios predicted using the thermal proton transfer model are similar to the experimental measurements, indicating that thermal proton transfer reactions play a major role in generating ions in ultraviolet-MALDI.n Graphical Abstractᅟ

On the inelastic impact of composite laminated plate and shell structures

Abstract The dynamic responses of composite laminated plates and shells due to inelastic impact are analyzed by using the finite element method. In the inelastic impact analysis, the structure is considered to be elastic, but the loading is idealized as inelastic. A modified isoparametric linear shell element, in which the shear deformation and rotatory inertia are taken into account, together with the theory of conservation of momentum and Newmark time integration method are used to solve the set of finite element equations. The influences of shell curvature on the impact response are investigated and discussed. The impact experiments are performed and the experimental results are in good agreement with the finite element solutions.

Is energy pooling necessary in ultraviolet matrix-assisted laser desorption/ionization?

RATIONALEnEnergy pooling has been suggested as the key process for generating the primary ions during ultraviolet matrix-assisted laser desorption/ionization (UV-MALDI). In previous studies, decreases in fluorescence quantum yields as laser fluence increased for 2-aminobenzoic acid, 2,5-dihydroxybenzoic acid (2,5-DHB), and 3-hydroxypicolinic acid were used as evidence of energy pooling. This work extends the research to other matrices and addresses whether energy pooling is a universal property in UV-MALDI.nnnMETHODSnEnergy pooling was investigated in a time-resolved fluorescence experiment by using a short laser pulse (355u2009nm, 20u2009ps pulse width) for excitation and a streak camera (1u2009ps time resolution) for fluorescence detection.nnnRESULTSnThe excited-state lifetime of 2,5-DHB decreased with increases in laser fluence. This suggests that a reaction occurs between two excited molecules, and that energy pooling may be one of the possible reactions. However, the excited-state lifetime of 2,4,6-trihydroxyacetophenone (THAP) did not change with increases in laser fluence. The upper limit of the energy pooling rate constant for THAP is estimated to be approximately 100-500 times smaller than that of 2,5-DHB.nnnCONCLUSIONSnThe small energy pooling rate constant for THAP indicates that the potential contribution of the energy pooling mechanism to the generation of THAP matrix primary ions should be reconsidered.

Static contact crushing of composite laminated shells

The crush behavior of carbon-epoxy composite laminated shells with three different curvatures is investigated. The FEM package ABAQUS and the user-defined material subroutine (UMAT) based on the concept of progressive stiffness degradation were employed to simulate crushing until the specimens totally collapsed. The 2-D delamination propagation proposed by Davies et al. is considered to be an additional failure mechanism for some curved shells whose contact crushing forces are large. The ultimate strengths of the shells are accurately predicted by the presented method, and all experimental cases are accurately simulated and explained.

Study on the compressive strength of laminated composite with through-the-width delamination

A nonlinear finite element code, DELAM3D, with a three-dimensional layered solid element based on the updated Lagragian formulation, is developed to simulate the compressive response of a laminated composite plate with multiple delaminations. An analytical model is established to characterize the mechanical behaviors such as postbuckling, contact of the delaminating interface, delamination growth and fiber-matrix failure. Double cantilever beam (DCB) and end notched flexure (ENF) tests, with T300/976 graphite/epoxy, are performed to verify the energy release rate of the material. Experiments with various crack numbers, sizes, locations and layer orientations have been conducted and compared with the numerical solution. Good agreement is expected.