Analysis of primary aromatic amines using precolumn derivatization by HPLC fluorescence detection and online MS identification

2-(2-Phenyl-1H-phenanthro-[9,10-d]imidazole-1-yl)-acetic acid (PPIA) and 2-(9-acridone)-acetic acid (AAA), two novel precolumn fluorescent derivatization reagents, have been developed and compared for analysis of primary aromatic amines by high performance liquid chromatographic fluorescence detection coupled with online mass spectrometric identification. PPIA and AAA react rapidly and smoothly with the aromatic amines on the basis of a condensation reaction using 1-ethyl-3-(3dimethylaminopropyl)-carbodiimide (EDC) as dehydrating catalyst to form stable derivatives with emission wavelengths at 380 and 440 nm, respectively. Taking six primary aromatic amines (aniline, 2-methylaniline, 2-methoxyaniline, 4-methylaniline, 4-chloroaniline, and 4-bromoaniline) as testing compounds, derivatization conditions such as coupling reagent, basic catalyst, reaction temperature and time, reaction solvent, and fluorescent labeling reagent concentration have also been investigated. With the better PPIA method, chromatographic separation of derivatized aromatic amines exhibited a good baseline resolution on an RP column. At the same time, by online mass spectrometric identification with atmospheric pressure chemical ionization (APCI) source in positive ion mode, the PPIA-labeled derivatives were characterized by easy-to-interpret mass spectra due to the prominent protonated molecular ion m/z [M + H](+) and specific fragment ions (MS/MS) m/z 335 and 295. The linear range is 24.41 fmol-200.0 pmol with correlation coefficients in the range of 0.9996-0.9999, and detection limits of PPIA-labeled aromatic amines are 0.12-0.21 nmol/L (S/N = 3). Method repeatability, precision, and recovery were evaluated and the results were excellent for the efficient HPLC analysis. The most important argument, however, was the high sensitivity and ease-of-handling of the PPIA method. Preliminary experiments with wastewater samples collected from the waterspout of a paper mill and its nearby soil where pollution with aromatic amines may be expected show that the method is highly validated with little interference in the chromatogram.

Determination of aliphatic amines from soil and wastewater of a paper mill by pre-column derivatization using HPLC and tandem mass spectrometry (HPLC-MS/MS)

A pre-column derivatization method for the sensitive determination of aliphatic amines using the labeling reagent 1,2-benzo-3,4-dihydrocarbazole-9-ethyl chloroformate (BCEOC) followed by HPLC with fluorescence detection and APCI/NIS identification in positive-ion mode has been developed. The chromophore of 2-(9-carbazole)-ethyl chloroformate (CEOC) reagent was replaced by the 1,2-benzo-3,4-dihydrocarbazole functional group, which resulted in a sensitive fluorescence derivatizing reagent, BCEOC, that could easily and quickly label amines. Derivatives were stable enough to be efficiently analyzed by HPLC and showed an intense protonated molecular ion corresponding m/z [M + H](+) with APCI/MS in positive-ion mode. The collision induced dissociation of the protonated molecular ion formed characteristic fragment ions at m/z 264.1, m/z 246.0 and m/z 218.1, corresponding to the cleavages of CH2CH2O-CO, CH2CH2-OCO, and N-CH2CH2O bonds. Studies on derivatization conditions demonstrated that excellent derivatization yields close to 100% were observed with a 3 to 4-fold molar reagent excess in acetonitrile solvent, in the presence of borate buffer (pH 9.0) at 40 degrees C for 10 min. In addition, the detection responses for BCEOC derivatives were compared with those obtained with CEOC and FMOC as labeling reagents. The ratios I-BCEOC/I-CEOC and I-BCEOC/I-FMOC were, respectively, 1.40-2.76 and 1.36-2.92 for fluorescence responses (here, I was the relative fluorescence intensity). Separation of the amine derivatives had been optimized on an Eclipse XDB-C-8 column. Detection limits calculated from an 0.10 pmol injection, at a signal-to-noise ratio of 3, were 18.65-38.82 fmol (injection volume 10 mu L for fluorescence detection. The relative standard deviations for intraday determination (n = 6) of standard amine derivatives (50 pmol) were 0.0063-0.037% for retention times and 3.36-6.93% for peak areas. The mean intra-and inter-assay precision for all amines were <5.4% and 5.8%, respectively. The recoveries of amines ranged from 96 to 113%. Excellent linear responses were observed with correlation coefficients of >0.9994. The established method provided a simple and highly sensitive technique for the quantitative analysis of trace amounts of aliphatic amines from biological and natural environmental samples.

The Liquefaction and Displacement of Highly Saturated Sand under Water Pressure Oscillation

In order to investigate the characteristics of water wave induced liquefaction in highly saturated sand in vertical direction, a one-dimensional model of highly saturated sand to water pressure oscillation is presented based oil the two-phase continuous media theory. The development of the effective stresses and the liquefaction thickness are analyzed. It is shown that water pressure oscillating loading affects liquefaction severely and the developing rate of liquefaction increases with the decreasing of the sand strength or the increasing of the loading strength. It is shown also that there is obvious phase lag in the sand Column. If the sand permeability is non-uniform, the pore pressure and the strain rise sharply at which the smallest permeability occurs. This solution may explain Why the fracture occurs in the sand column in some conditions.

Rapidly Infrared-Assisted Cooperatively Self-Assembled Highly Ordered Multiscale Porous Materials

In this paper, cooperative self-assembly (CSA) of colloidal spheres with different sizes was studied. It was found that a complicated jamming effect makes it difficult to achieve an optimal self-assembling condition for construction of a well-ordered stacking of colloidal spheres in a relatively short growth time by CSA. Through the use of a characteristic infrared (IR) technique to significantly accelerate local evaporation on the growing interface without changing the bulk growing environment, a concise three-parameter (temperature, pressure, and IR intensity) CSA method to effectively overcome the jamming effect has been developed. Mono- and multiscale inverse opals in a large range of lattice scales can be prepared within a growth time (15-30 min) that is remarkably shorter than the growth times of several hours for previous methods. Scanning electron microscopy images and transmittance spectra demonstrated the superior crystalline and optical qualities of the resulting materials. More importantly, the new method enables optimal conditions for CSA without limitations on sizes and materials of multiple colloids. This strategy not only makes a meaningful advance in the applicability and universality of colloidal crystals and ordered porous materials but also can be an inspiration to the self-assembly systems widely used in many other fields, such as nanotechnology and molecular bioengineering.

Directly synthesized strong, highly conducting, transparent single-walled carbon nanotube films

We report the direct synthesis of strong, highly conducting, and transparent single-walled carbon nanotube (SWNT) films. Systematically, tests reveal that the directly synthesized films have superior electrical and mechanical properties compared with the films made from a solution-based filtration process: the electrical conductivity is over 2000 S/cm and the strength can reach 360 MPa. These values are both enhanced by more than 1 order. We attribute these intriguing properties to the good and long interbundle connections. Moreover, by the help of an extrapolated Weibull theory, we verify the feasibility of reducing the interbundle slip by utilizing the long-range intertube friction and estimate the ultimate strength of macroscale SWNTs without binding agent.

Pure Coulomb explosions of highly charged methane clusters investigated by a simple electrostatic model

The pure Coulomb explosions of the methane clusters (CA(4))(n), (light atom A = H or D) have been investigated by a simplified electrostatic model for both a single cluster and an ensemble of clusters with a given cluster size distribution. The dependence of the energy of ions produced from the explosions on cluster size and the charge state of the carbon ions has been analysed. It is found that, unlike the average proton energy which increases with the charge q of the carbon ions, the average deuteron energy tends to saturate as q becomes larger than 4. This implies that when the laser intensity is sufficiently high for the (CD4)(n) to be ionized to a charge state of (C4+D4+)(n), the neutron yield from a table-top laser-driven Coulomb explosion of deuterated methane clusters (CD4)(n) could be increased significantly by increasing the interaction volume rather than by increasing the laser intensity to produce the higher charge state (C6+D4+)(n). The flight-time spectra of the carbon ions and the light ions have also been studied.

Highly sensitive wave-front sensor with a non-zero-order phase plate

We propose a novel highly sensitive wave front detection method for a quick check of a flat wave front by taking advantage of a non-zero-order pi phase plate that yields a non-zero-order diffraction pattern. When a light beam with a flat wave front illuminates a phase plate, the zero-order intensity is zero. When there is a slight distortion of the wave front, the zero-order intensity increases. The ratio of first-order intensity to that of zero-order intensity is used as the criterion with which to judge whether the wave front under test is flat, eliminating the influence of background light. Experimental results demonstrate that this method is efficient, robust, and cost-effective and should be highly interesting for a quick check of a flat wave front of a large-aperture laser beam and adaptive optical systems. (c) 2005 Optical Society of America.

Design of a highly stable, high-conversion-efficiency pumping source for optical parametric amplifier by extending efficient crystal length

The objective of this study is to improve the stability of pumping source of optical parametric amplifier. Analysis by simulation leads to the conclusion that the stability of the second harmonic can be improved by using properly the intensity of fundamental light and corresponding length of the crystal. By the method of the noncollinear two-pass second harmonic or the tandem second harmonic, the efficient crystal length is extended to a proper value, and the stability of the second harmonic output has been improved two times more than that for the fundamental light, and the conversion-efficiency is about 70% in experiment. When the variation of the fundamental light is about 10%, the variation of the second harmonic intensity has been controlled within 5%. (c) 2006 Elsevier Ltd. All rights reserved.

Highly stable, diode-pumped Nd : YLF regenerative amplifier

We present the design and experimental results for a diode pumped Nd:YLF regenerative amplifier applied to amplify a nanosecond laser pulse. Numerical simulation shows that the maximum output energy and the best stability can be obtained when the regenerative amplifier operates in a saturated mode for all pulse duration and temporal profiles. Using extra post-pulse is a good method to decrease the square-pulse distortion caused by gain saturation effect. The amplifier shows output energy of 4.2mJ with a total energy gain of more than 107 and output energy stability of better than 1% rms. When extra post-pulse is added, square-pulse distortion is decreased from 1.33 to 1.17 for the amplifier that is seeded with an optical pulse of 3 ns.

A humidity-resistant highly sensitive holographic photopolymerizable dry film

A new humidity-resistant highly sensitive acrylamide-based photopolymeric holographic recording material has been developed. The photopolymer is resistant to the humidity of environment. Diffraction efficiencies near 50% are obtained with exposure energy of 60 mJ/cm(2) in materials of 150 mu m. thickness. Diphenyl iodonium chloride is added to the material and can increase the exposure sensitivity by a factor of more than 4 (to about 28 mJ/cm(2)). An image has been successfully stored in the material with a small distortion. (C) 2005 Elsevier B.V. All rights reserved.

Highly efficient Nd:YAG ceramic CW laser with 59.8% slope-efficiency

In this paper, a highly efficient Ti:sapphire end-pumped 1 at.-% Nd:YAG ceramic laser that is comparable in efficiency with Nd:YAG single crystal lasers has been developed. Optical absorption and emission spectra for Nd:YAG ceramics have been measured. With 673-mW pumping, 295-mW laser output at 1064 nm has been obtained. The laser threshold is only 13 mW. Deducted the transmitted light, the corresponding optical-to-optical conversion efficiency is 58.4%. The lasing characteristics of Nd:YAG ceramic are nearly equal to those of Nd:YAG single crystal.

Highly efficient diode side-pumped Nd : YAG ceramic laser with 210W output power

We developed a highly efficient diode side-pumped Nd:YAG ceramic laser with a diffusive reflector as an optical pump cavity. A maximum output power of 211.6W was obtained with an optical -to- optical conversion efficiency of 48.7%. This corresponds to the highest conversion efficiency in the side-pumped ceramic rod. Thermal effects of the Nd:YAG ceramic rod were analyzed in detail through the measurements of laser output powers and beam profiles near the critically unstable region. A M-2 beam quality factor of 18.7 was obtained at the maximum laser output power. (c) 2006 Elsevier Ltd. All rights reserved.