Determination and confirmation of malachite green and leucomalachite green residues in salmon using liquid chromatography/mass spectrometry with no-discharge atmospheric pressure chemical ionization

A liquid chromatography/mass spectrometry (LC/MS) method was developed to quantitate and confirm residues of leucomalachite green (LMG) in salmon tissue after their conversion to chromic malachite green (MG) in the extraction process. The method uses no-discharge atmospheric pressure chemical ionization (APCI) in conjunction with an ion-trap instrument to generate product-ion spectra. In the sample preparation procedure, salmon tissue is extracted with acetonitrile/buffer, the LMG residue is partitioned into methylene chloride, the LMG is converted to MG using an organic oxidizing agent, and the MG is isolated on alumina/propylsulfonic acid solid-phase extraction cartridges. The method was validated by fortifying salmon with different levels of LMG, and then detecting the residue as MG The LC/MS conditions, including a comparison of electrospray and no-discharge APCI, were evaluated and optimized. MG was not confirmed in any of the control tissue extracts, and all fortified samples analyzed during validation met the confirmation criteria as described. In addition to providing confirmatory data, this method can provide an alternative method for quantitation of MG in salmon. The recoveries of LMG measured as MG by this LC/MS method, at fortification levels of 1-10 ng/g were very high (86-109%), with low relative standard deviation(RSD) values (6.4-13%). The results agreed very closely with those obtained for the same extracts using an LCNIS procedure, indicating that matrix suppression was not an issue. The presence of LMG in salmon tissue samples fortified at 0.25 ng/g was confirmed by this method, with an average recovery of 70.1% and an RSD of 12.0%. Sample extracts from fish exposed to MG were also analyzed.     

Electrochemical synthesis of nanostructured ZnO films utilizing self-assembly of surfactant molecules at solid-liquid interfaces

An electrochemical synthesis strategy for the production of nanostructured films was developed by combining self-assembly of surfactant-inorganic aggregates at solid-liquid interfaces and an electrodeposition process. Through this approach high quality nanostructured ZnO films were cathodically deposited from a plating solution containing 0.1 wt % of sodium dodecyl sulfate (SDS). The resulting ZnO films possess lamellar structures with two different repeat distances, d001 = 31.7 A and d001* = 27.5 A, both of which feature well-defined long range order. Due to kinetically controlled surfactant-inorganic assembly during the deposition process, the film exhibits a wide distribution of the stacking directions of the ZnO layers, which will allow facile access of the guest molecules and analytes to the interlayers. The synthetic mechanism used here can be generalized to generate nanostructured films of other semiconducting and metallic materials with architectures that cannot be assembled by other means.     

Fluorescent signaling based on control of excited state dynamics. Biarylacetylene fluorescent chemosensors

We have previously reported that metal ion binding could restrict the excited state rotation of a biaryl chromophore, suppressing intersystem crossing and leading to increased emission. We have now applied the restriction of excited state dynamics to suppression of the other fundamental nonradiative decay pathway, internal conversion, in biarylacetylenes. This indicates that both nonradiative decay pathways are subject to conformational control, and that this signaling pathway should be generally accessible in simple flexible fluorophores.     

Liquid chromatographic determination of diminazene diaceturate (Berenil) in raw bovine milk

A simple liquid chromatographic (LC) method is presented for the determination of diminazene (DZ) in raw bovine milk. DZ is extracted from raw milk by chilled aqueous centrifugation and is isolated from milk components on a cyano solid-phase extraction column. DZ is eluted by using a methanol-ion pairing reagent. A Phenomenex LUNA CN column and an acetonitrile-buffered mobile phase with a counter ion are used for gradient LC. The LC effluent is monitored at a detection wavelength of 372 nm by using a deuterium lamp. Under the parameters described, the retention time of DZ is 8-10 min with a peak area response of 6.5 mAU/ng. The method demonstrated excellent precision over all levels tested (25-400 ppb) with an overall average recovery of 90.4 +/- 14.5%. The method is applicable to the monitoring of milk for DZ residues at the 25 ppb level with a limit of quantitation of 10 ppb.