A Method for Determination of Low Levels of Exposure to 2,4-D and 2,4,5-T

A method has been developed for the determination of trace quantities of 2,4-dichloro-phenoxyacetic acid (2,4-D), 2,4,5-trichlorophenoxyacetic acid (2,4,5-T), 2,4-dichlorophenol (2,4-DCP), and 2,4,5-trichlorophenol (2,4,5-TCP) in human and rat urine. The method involves acid hydrolysis of the phenolic conjugates, extraction of the free phenols and acids, ethylation with diazoethane, silica-gel column chromatography clean-up of the derivatized urine extract, and gas chromatographic determination using the electron-capture detector. The average recoveries of 2,4-D, 2,4,5-T, 2,4-DCP, and 2,4,5-TCP from rat urine spiked with known amounts of the herbicides and their phenols were 94%, 98%, 92%, and 90%, respectively. The limits of detection for 2,4-D, 2,4,5-T, DCP, and TCP in rat urine were: 0.05, 0.01, 0.10, and 0.01 ppm, respectively. The method was used to analyze urine of rats given various levels of 2,4-D and 2,4,5-T by gavage. Results showed that levels of exposure of 3.75 mcg/kg for 2,4-D and 5.0 mcg/kg for 2,4,5-T in rats can be detected in urine within 24 hr from exposure. Urine samples from occupationally exposed people were analyzed and found to contain 0.2 to 1.0 ppm 2,4-D and 0.05 to 3.6 ppm 2,4,5-T.     

Synthesis of the One-dimensional Compound (Ph4P)[In(P2Se6)] in a Ph4P+-Containing Selenophosphate Flux,and Structure of [In(P2Se6)2]5– – a Discrete Molecular Fragment of the [In(P2Se6)]nn– Chain

The reaction of one equivalent of In with a molten flux of (Ph₄P)₂Se₅ and P₂Se₅ (1 : 2), at 250 °C gave the (Ph₄P)[In(P₂Se₆)] ( I ). Stoichiometric elemental synthesis at 750 °C produced the Cs₅In(P₂Se₆)₂ ( II ). The thin, yellow crystals of ( I ), and the irregular, dark orange crystals of ( II ), appear to be air- and water-stable. Compound ( I ) crystallizes in the monoclinic space group C2/c (no. 15) and at 23 °C: a = 23.127(7) Å, b = 6.564(1) Å, c = 19.083(3) Å, β = 97.42(2)°, V = 2873(1) ų, Z = 4, final R/R_w = 4.4/5.2%. Compound ( II ) crystallizes in the tetragonal space group P4₂/m (no. 84) and at 23 °C: a = b = 13.886(1) Å, c = 7.597(2) Å, V = 1464.9(3) ų, Z = 2, final R/R_w = 3.9/5.1%. Compound ( I ) contains infinite [In(P₂Se₆)]_n^n– with a structure related to that of K₂FeP₂Se₆. Compound ( II ) contains the discrete [In(P₂Se₆)₂]^5– which can be viewed as a fragment of the [In(P₂Se₆)]_n^n– chain.     

The development and validation of a high performance liquid chromatography (HPLC)/tandem mass spectrometry assay for fenticonazole in human plasma and comparison with an HPLC-UV method

A method is described for the determination of fenticonazole in human female plasma. The method utilizes high performance liquid chromatography coupled to atmospheric pressure positive-ion chemical ionization triple quadrupole mass spectrometry. Multiple reaction monitoring is employed for selectivity and sensitivity which enables quantification over the range 0.5–20 ng mL⁻¹ with acceptable precision and accuracy. A comparison is made with an existing HPLC-UV assay and the utility of the technology of combined liquid chromatography and tandem mass spectrometry for subnanogram per mL assays is discussed.     

An iterative rational fraction polynomial technique for modal identification

The rational fraction polynomial (RFP) modal identification procedure is a well known frequency domain fitting technique. To deal with a linear problem, the RFP procedure does not directly minimize the fitting error, i.e. the difference between the experimental and the analytical frequency response function, but a frequency weighted function of it: this causes bias in the modal parameter estimates. In this paper an iteration procedure is proposed which uses the output of the RFP technique as a starting estimate, and minimizes the true fitting error, expressed as a first order Taylor expansion of the identified parameters. Results are quite satisfactory: the fitting error is notably reduced after few iterations. Moreover, less computational modes with respect to the original RFP method are needed to obtain a good fit in a given frequency band.A first version of this paper was presented at 17th Int. Seminar on Modal Analysis, Leuven (Belgium), 23–25 September 1992, and preprinted in the Proceedings.     

A third order scheme in the vlasov theory and some consequences in the evolution of few body systems

Summary A set of implemented evolution equations, describing the coherent nonlinear interaction of plasma waves, based on the perturbation method, has been derived, taking into account initial value effects and third order nonlinearities in the modal amplitudes.The equations reduce, in the appropriate limit, to well known stochastic triplets of hydrodynamic type.It is argued that, the stochastization mechanism of the decay instability in strongly damped regime, may be interpreted as a Duffing-type behavior.

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Sommario Si presenta un sistema di equazioni di evoluzione descrivente l'interazione coerente nonlineare di onde di plasma, tenendo conto di effetti di condizioni iniziali e nonlinearità del terzo ordine nelle ampiezze modali. Le equazioni si riducono, nel limite appropriato, a ben noti tripletti stocastici di tipo idrodinamico.Si ipotizza che il processo di stocastizzazione della instabilità di decadimento, in regime di forte dissipazione, possa essere interpretato da un modello dinamico del tipo Duffing.

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Lyst of greek symbols omega (lower case)=frequency - delta (1.c.)=partial derivative - pi (1.c.)=greek pi (=3,14r. units) in (26) - Sigma (Capital case)=Summation symbol - Delta (C.c)=def. as in (14) - epsilon (1.c.) def. as in (10) - sigma (1.c.)=def. as in (36) - gamma (1.c.)=def. as in (37) - beta (1.c.)=def. as in (37) - ro, (1.c.)=def. as in (37) - alfa (1.c.)=def. in connection with _k in (60) - Gamma (C.c.)=def. as in (63) and (66), (67) - delta (1.c.)=def. as in (66) - psi (1.c.)=def. as in (75) - fi (1.c.)=def. in (71) in connection with ₀ - Fi (C.c.)=def. as in (75) - Omega (C.c.)=def. in (78)     

Artocarpus plants as a potential source of skin whitening agents

Artocarpus plants have been a focus of constant attention due to the potential for skin whitening agents. In the in vitro experiment, compounds from the Artocarpus plants, such as artocarpanone, norartocarpetin, artocarpesin, artogomezianol, andalasin, artocarbene, and chlorophorin showed tyrosinase inhibitory activity. Structure-activity investigations revealed that the 4-substituted resorcinol moiety in these compounds was responsible for their potent inhibitory activities on tyrosinase. In the in vitro assay, using B16 melanoma cells, the prenylated polyphenols isolated from Artocarpus plants, such as artocarpin, cudraflavone C, 6-prenylapigenin, kuwanon C, norartocarpin, albanin A, cudraflavone B, and brosimone I showed potent inhibitory activity on melanin formation. Structure-activity investigations revealed that the introduction of an isoprenoid moiety to a non-isoprenoid-substituted polyphenol enhanced the inhibitory activity of melanin production in B16 melanoma cells. In the in vivo investigation, the extract of the wood of Artocarpus incisus and a representative isolated compound from it, artocarpin had a lightening effect on the skin of guinea pigs' backs. Other in vivo experiments using human volunteers have shown that water extract of Artocarpus lakoocha reduced the melanin formation in the skin of volunteers. These results indicate that the extracts of Artocarpus plants are potential sources for skin whitening agents.     

Analysis of coumarin and angelica lactones in smokeless tobacco products

Differences in health risks between different styles of smokeless tobacco products (STPs) have prompted interest in their relative levels of toxic chemicals. We report here the development of methods for the analysis of STPs for coumarin and for α-angelica lactone (α-AL), both of which have been included in various published lists of tobacco toxicants. We have also determined the concentrations of these lactones in commercial STPs from the US and Sweden, representing 80–90% of the 2010 market share for all the major STP categories in these two countries: 65 products (plus two reference products) for coumarin and 66 commercial products for α-AL. For coumarin, methanol extracts of the STPs were analysed by HPLC/MS/MS. The lower limit of quantification (LOQ) and limit of detection (LOD) were, respectively, 100 and 30 ng coumarin/g of STP on a wet weight basis (WWB). Alpha-AL was determined via direct headspace GC/MS. The LOQ and LOD were 65 and 30 ng/g WWB respectively. Coumarin was detected In 3/33 Swedish snus, 5/13 US chewing tobaccos, 16/16 moist snuffs and 5/6 dry snuffs. Concentrations in those samples with quantifiable coumarin contents ranged from 186 to 1656 ng/g WWB. Concentrations of coumarin measured in this study were consistent with levels naturally found in tobacco. None of the STPs analysed would significantly contribute to coumarin exposure in consumers compared with dietary sources, and estimated exposure levels were 1000× lower than the European Food Safety Authority Tolerable Daily Intake. Hence the relevance of coumarin to the toxicity of STPs and its inclusion in the FDA’s list of harmful and potentially harmful compounds list is questionable. Measurements of α-AL in these STPs found that the majority did not have quantifiable contents, however, for three STPs concentrations of α-AL were above the LOQ (116–140 ng/g WWB) and for four other STPs concentrations of α-AL could be estimated between the LOD and LOQ. Beta-angelica lactone was tentatively identified in three of the STPs but the levels could not be reliably quantified. The levels of α-AL in tobacco products are reported here for the first time, but the relevance of α-AL to the toxicity of STPs is also highly questionable given that it has GRAS status as a permitted food additive.     

Experimental modal analysis and damage detection on an ancient masonry building

Procedures and results are presented relative to the modal identification of an old masonry building from two sets of experimentally determined frequency-response functions. Both tests were performed by exciting the structure with low-intensity forces produced by a vibrodyne, before and after high-intensity shakes comparable to a destructive earthquake, in crder to detect and quantify the damage suffered by the masonry. In spite of non-linearities appearing in the frequency response functions, a significant modal model is obtained in both cases, provided that a non-proportional damping model, yielding complex modes, is adopted. The decreasing of natural frequencies, in addition to the increasing of damping factors between the two low-intensity tests, indicate remarkable structural damage. In order to obtain useful quantities for the identification of a finite element model, which is the most suited for damage localization and quantification, real modes have been extracted by filtering out the damping effects from the complex modes derived by appropriately curve-fitting the frequency-response functions.

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Sommario Si presentano le metodologie ed i risultati dell'identificazione delle grandezze modali di un vecchio edificio in muratura per due serie di misure sperimentali di risposta in frequenza. Esse sono ottenute eccitando l'edificio con forze di bassa intensita indotte da una vibrodina, prima e dopo una serie di altre prove sperimentali condotte con forze dinamiche di alta intensità, con l'obiettivo di quantificare il danneggiamento subito dalle strutture murarie. La presenza di non linearita, evidente anche nelle risposte in frequenza, non ha impedito di ricavare un modello modale soddisfacente, adottando pero modi complessi, a cui corrisponde un modello non proporzionaleper lo smorzamento. La diminuzione delle frequenze proprie e l'aumento degli smorzamenti modali, tra la prima e la seconda serie di prove, mostra che il danneggiamento della struttura e stato notevole. Per ottenere grandezze utili all'identilicazione di un modello agli elementi finiti, più adatto alla localizzazione e alla quantificazione del danneggiamento, si sono ricavati modi reali eliminando l'effetto dello smorzamento non proporzionale dai modi complessi ottenuti dalle funzioni di risposta in frequenza.

     

Energy studies of atomic atmospheric ions in collisions with molecular nitrogen and oxygen

Studies of internal energy changes between the partners in ion-molecule collisions can be facilitated by high-resolution translational energy spectroscopy. Collisions of keV H⁺, N⁺ and O⁺ on molecular nitrogen and oxygen have shown that for 30 reaction channels all are consistent with spin conservation, which has not been generally acknowledged in previous studies. Estimations of the fractional metastable composition in each ion beam have also been made.