Determination of chlorantraniliprole residues in crops by liquid chromatography coupled with atmospheric pressure chemical ionization mass spectrometry/mass spectrometry

An analytical method is presented for the determination of chlorantraniliprole residues in crops. Chlorantraniliprole residues were extracted from crop matrixes with acetonitrile after a water soak. The extracts were passed through a strong anion-exchange (SAX) SPE cartridge stacked on top of a reversed-phase (RP) polymer cartridge. After both cartridges were rinsed and vacuum-dried, the SAX cartridge was removed, and chlorantraniliprole was eluted from the RP polymer cartridge with acetonitrile. The acetonitrile eluate was evaporated to dryness, reconstituted, and analyzed using an LC/MS/MS instrument equipped with an atmospheric pressure chemical ionization source. The method was successfully validated at 0.010, 0.10, and 10 mg/kg for the following crop matrixes: potatoes, sugar beets (tops), lettuce, broccoli, soybeans, soybean forage, tomatoes, cucumbers, oranges, apples, pears, peaches, almonds (nutmeat), rice grain, wheat grain, wheat hay, corn stover, alfalfa forage, cottonseed, grapes, and corn grain. The average recoveries from all crop samples fortified at the method LOQ ranged from 91 to 108%, with an overall average recovery of 97%. The average recoveries from all crop samples fortified at 10 times the method LOQ ranged from 89 to 115%, with an overall average recovery of 101%. For all of the fortified control samples analyzed in this study, the overall average recovery was 99%.     

Kinetics of Er3+-doped fluorozirconate optical fiber upconversion fluorescence and laser emission under 800 nm excitation

Applying single- and double-pulse excitation at 800 nm, the kinetics of the upconversion fluorescence in the green, as well as the upconversion laser at 543 nm was studied. No significant delay between the pumping pulse and the laser emission was found. In the erbium doped (1000 ppm) optical fiber, the mechanism responsible for the upconversion is purely of the excited state absorption (ESA) type. The double-pulse technique enables also a determination of the lifetime of the intermediate metastable state ⁴ I _11/2 (7±0.3 ms). Some other basic properties of the upconverted fluorescence and of the laser itself (fluorescence spectrum, optical gain, laser threshold) are also described. Received: 11 December 2000 / Revised version: 18 February 2001 / Published online: 18 July 2001     

Widely tunable diffraction limited 1000 mW external cavity diode laser in Littman/Metcalf configuration for cavity ring-down spectroscopy

We report on recent progress on external cavity diode lasers (ECDL) using a new concept of a Littman/Metcalf configuration. Within this concept one facet of the diode laser chip is used for coupling to a high quality Littman/Metcalf resonator whereas the other side of the diode laser chip emits the output beam. The alignment of the external resonator is independent from the alignment of the output beam and there is no need for any compromise in the alignment. This results in an improved behavior of the external resonator with the benefit of a drastic increase in power and single mode tuning.We investigated this light source for high resolution spectroscopy in the field of cw-cavity ring-down spectroscopy (CRDS). The monitoring of environmental and medical gases from vehicles or human breath requires a suitable radiation source in the mid-infrared (MIR) between 3 and 5 μm that is frequency stable and can be widely tuned. Since this wavelength cannot be reached via direct emitting room temperature semiconductor lasers, additional techniques like difference frequency generation (DFG) are essential. Tunable difference frequency generation relies on high power, small linewidth, fast tunable, robust laser diode sources with excellent beam quality.With our new compact, alignment-insensitive and robust ECDL concept, we achieved an output power of 1000 mW and an almost Gaussian shaped beam quality (M²<1.2). The coupling efficiency for optical waveguides as well as single mode fibers exceeds 70%. The wavelength is widely tunable within the tuning range of 20 nm via remote control. This laser system operates longitudinally in single mode with a mode-hop free tuning range of more than 150 GHz without current compensation and a side-mode-suppression better than 50 dB. This concept is currently realized within the wavelength regime between 750 and 1080 nm.Our high powered Littman/Metcalf laser system was part of a MIR-light source which utilizes DFG in periodically poled lithium niobate (PPLN) crystals. At the wavelength of 3.3 μm we were able to achieve a high-resolution absorption spectrum of water with four different isotoplogues of H₂O components. This application clearly demonstrates the suitability of this laser for high-precision measurements. PACS 07.57.Ty; 42.55.Px; 42.62.Fi     

Preparation and characterization of uranyl complexes with phosphonate ligands

The preparation, spectroscopic characterization and thermal stability of neutral complexes of uranyl ion, UO₂ ²⁺, with phosphonate ligands, such as diphenylphosphonic acid (DPhP), diphenyl phosphate (DPhPO) and phenylphosphonic acid (PhP) are described. The complexes were prepared by a reaction of hydrated uranyl nitrate with appropriate ligands in methanolic solution. The ligands studied and their uranyl complexes were characterized using thermogravimetric and elemental analyses, ESI-MS, IR and UV–Vis absorption and luminescence spectroscopy as well as luminescence lifetime measurements. Compositions of the products obtained dependent on the ligands used: DPhP and DPhPO form UO₂L₂ type of complexes, whereas PhP forms UO₂L complex. Based on TG and DTG curves a thermal stability of the complexes was determined. The complexes UO₂PhP·2H₂O and UO₂(DPhPO)₂ undergo one-step decomposition, while UO₂PhP · 2H₂O is decomposed in a two-step process. The thermal stability of anhydrous uranyl complexes increases in the series: DPhPO < PhP < DPhP. Obtained IR spectra indicate bonding of P–OH groups with uranyl ion. The main fluorescence emission bands and the lifetimes of these complexes were determined. The complex of DPhP shows a green uranyl luminescence, while the uranyl emission of the UO₂PhP and UO₂(DPhPO)₂ complexes is considerably weaker.     

Synthesis, spectroscopic and structural properties of uranyl complexes based on bipyridine N-oxide ligands

By using 2,2′-bipyridine N-oxide (bipyO) and 2,2′-bipyridine N,N′-dioxide (bipyO₂), three new uranyl complexes [UO₂(bipyO)SO₄]·H₂O (1), [UO₂(bipyO)(OH)(NO₃)]₂·H₂O (2) and [UO₂(bipyO₂)H₂O](ClO₄)₂·(3) were synthesized using uranyl salts including non-coordinating or weakly coordinating power of the ClO₄⁻ anion and the strongly coordinating power of NO₃⁻ and SO₄²⁻ anions. All of the compounds were characterized by CHN microanalytical procedures, infrared and luminescence spectroscopy and by single crystal X-ray diffraction. Spectroscopic studies indicate that the bipyO is bound to the uranyl group via the nitrogen and oxygen atoms. Structural analyses revealed that overall bonding pattern is different in each case: 1 is a polymer; in 2 dimeric complex molecules are formed, whereas 3 is composed of monomers. In all of the complexes, the uranium atom is in a seven-coordinate environment.     

An experimental study of nonlinear dynamic system identification

A technique for robust identification of nonlinear dynamic systems is developed and illustrated using both digital simulations and analog experiments. The technique is based on the Minimum Model Error optimal estimation approach. A detailed literature review is included in which fundamental differences between the current approach and previous work is described. The most significant feature of the current work is the ability to identify nonlinear dynamic systems without prior assumptions regarding the form of the nonlinearities, in contrast to existing nonlinear identification approaches which usually require detailed assumptions of the nonlinearities. The example illustrations indicate that the method is robust with respect to prior ignorance of the model, and with respect to measurement noise, measurement frequency, and measurement record length.     

Experimental investigation of high-mach-number 3D hydrodynamic jets at the national ignition facility

The first hydrodynamic experiments were performed on the National Ignition Facility. A supersonic jet was formed via the interaction of a laser driven shock ( approximately 40 Mbar) with 2D and 3D density perturbations. The temporal evolution of the jet's spatial scales and ejected mass were measured with point-projection x-ray radiography. Measurements of the large-scale features and mass are in good agreement with 2D and 3D numerical simulations. These experiments provide quantitative data on the evolution of 3D supersonic jets and provide insight into their 3D behavior.     

Coupling of size-exclusion chromatography to liquid chromatography/mass spectrometry for determination of trace levels of thifensulfuron-methyl and tribenuron-methyl in cottonseed and cotton gin trash

Size-exclusion chromatography (SEC) was coupled to reversed-phase liquid chromatography/mass spectrometry for the determination of thifensulfuron-methyl and tribenuron-methyl in cottonseed and cotton gin trash. The limit of quantitation was 20 parts per billion (ppb), and the limit of detection was 6 ppb. The analytes were extracted by homogenization in a buffer solution. The extracts underwent a solvent exchange into methanol and were injected onto an SEC column. As the analytes eluted from the SEC column, the eluate was diverted onto a reversed-phase column for additional separation of the analytes and their detection via mass spectrometry. This method is unique because the samples are not cleaned up before analysis, the analytes are injected in methanol, and the entire analysis is completed in 30 min. Average recoveries and standard deviations for thifensulfuronmethyl and tribenuron-methyl in cotton gin trash were 91 +/- 6% and 88 +/- 5%, respectively. Average recoveries and standard deviations for thifensulfuron-methyl and tribenuron-methyl in cottonseed were 91 +/- 11% and 99 +/- 12%, respectively. This is an effective method for the detection and determination of thifensulfuron-methyl and tribenuron-methyl in cotton.