Improved luminescence properties of MoS2 monolayers grown via MOCVD: role of pre-treatment and growth parameters.

Fabrication of transition metal dichalcogenides (TMDCs) via metalorganic chemical vapor deposition (MOCVD) represents one of the most attractive routes to large-scale 2D material layers. Although good homogeneity and electrical conductance have been reported recently, the relation between growth parameters and photoluminescence (PL) intensity-one of the most important parameters for optoelectronic applications-has not yet been discussed for MOCVD TMDCs. In this work, MoS2 is grown via MOCVD on sapphire (0001) substrates using molybdenum hexacarbonyl (Mo(CO)6, MCO) and di-tert-butyl sulphide as precursor materials. A prebake step under H2 atmosphere combined with a reduced MCO precursor flow increases the crystal grain size by one order of magnitude and strongly enhances PL intensity with a clear correlation to the grain size. A decrease of the linewidth of both Raman resonances and PL spectra down to full width at half maxima of 3.2 cm-1 for the E 2g Raman mode and 60 meV for the overall PL spectrum indicate a reduced defect density at optimized growth conditions.

Structural assignment of isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids by liquid chromatography electrospray and atmospheric pressure chemical ionization tandem mass spectrometry.

Positionally isomeric 2-(2-quinolinyl)-1H-indene-1,3(2H)-dione mono- and disulfonic acids give rise to similar electrospray ionization (ESI) and atmosphere pressure chemical ionization (APCI) mass spectra, which show very abundant MH(+) ions and negligible fragmentation. The MH(+) ions of these isomeric acids exhibit notably different behavior under collision-induced dissociation (CID) conditions. The acids with a sulfonic group at position 8' in the quinoline moiety, adjacent to the N-atom, exhibit highly abundant [MH - H(2)SO(3)](+) ions (m/z 272 for the mono- and m/z 352 for the disulfonic acids), which are of lower abundance in the CID spectra of isomers with the SO(3)H group at other positions, remote from the nitrogen atom. The latter isomers undergo efficient eliminations of SO(3) and HSO(3). The isomeric diacids with one SO(3)H group at position 4 of the indene-1,3(2H)-dione moiety, adjacent to one of the carbonyl groups, undergo highly efficient elimination of H(2)O. Mechanistic pathways, involving interactions between adjacent groups, are proposed for the above regiospecific fragmentations. Pronounced different behavior has been also observed in negative ion tandem mass spectrometric measurements of the sulfonic acids. The distinctive behavior of the isomeric acids was strongly pronounced when the measurements were performed with an ion trap mass spectrometer (LCQ), and much less so with a triple-stage quadrupole instrument (TSQ).

Rapid quantification of hexachlorobenzene in the color additives D&C Red Nos. 27 and 28 (phloxine B) using solid-phase microextraction and gas chromatography-mass spectrometry.

The present paper describes the development of a method for the quantification of hexachlorobenzene (HCB) in the color additives D&C Red Nos. 27 and 28 (phloxine B) using solid-phase microextraction followed by gas chromatography-mass spectrometry (GC-MS) analysis. The method is simple and fast (1 h for each analysis), generates little solvent waste, and does not involve a solid matrix, thus permitting a more efficient extraction than does a previously developed Soxhlet extraction-GC-MS method. Test portions from 30 batches of US-certified color additives D&C Red Nos. 27 and 28 were analyzed for HCB using the new method. Those batches represent domestic (five) and foreign (one) manufacturers that requested certification for the colors during the past four years. All the samples contained HCB, ranging from 0.2 ppm to 244.3 ppm. The analyses revealed significant differences in the levels of HCB across batches from the same manufacturer as well as among different manufacturers. The range of HCB levels found in the analyzed batches (0.2-244.3 ppm) suggest that the contamination with HCB may be decreased by avoiding use of starting material (tetrachlorophthalic anhydride) heavily contaminated with HCB.

Tandem-in-time mass spectrometry method for the sub-parts-per-trillion determination of 2,3,7,8-chlorine-substituted dibenzo-p-dioxins and -furans in high-fat foods.

Limits of quantitation (LOQs) for a quadrupole ion storage tandem-in-time mass spectrometry (QISTMS) method were evaluated through replicate analysis of unfortified peanut oil, shortening, lamb fat, and butter for all 2,3,7,8-chlorine-substituted polychlorodibenzo-p-dioxins (PCDDs) and polychlorodibenzofurans (PCDFs). Ten congeners were measurable in butter (0.27-2.5 pg/g) and nine congeners were measurable in lamb fat (0.09-2.6 pg/g) with good precision. LOQs for high-fat foods were estimated by triplicate analysis of peanut oil fortified at two levels. Accurate and reproducible results were achieved at 0.5 pg/g for most PCDD/Fs (1.0 pg/g for heptachlorodibenzo-p-dioxin and heptachlorodibenzofuran and 2.0 pg/g for octachlorodibenzofuran) and at 0.2 pg/g for 2,3,7,8-tetrachlorodibenzofuran (TCDF) and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). QISTMS distinguished between catfish and chicken eggs with elevated TCDD levels from background samples collected from the most regions of the continental United States. QISTMS determined the extent of TCDD contamination in butter, lamb fat, and cottonseed oil collected from rural villages in Kazakhstan. Replicate analysis of catfish and chicken eggs by the QISTMS method produced comparable results to high-resolution mass spectrometry (HRMS). Lower limits of detection will be needed if QISTMS is to fully complement HRMS in the measurement of TCDD levels in food.

Fragmentation of isomeric N-quinolinylphthalimides on electron impact ionization.

The isomeric 2-, 3-, 5-, 6- and 8-quinolinylphthalimides give rise to different electron impact ionization mass spectra, which permit easy distinction. The specific fragmentation process are rationalized in terms of proximity effects and stabilization of cyclic ion structures. Collision-induced dissociation spectra were used to support the proposed ion structures of major fragment ions.

Preparative separation of components of the color additive D&C Red No. 28 (phloxine B) by pH-zone-refining counter-current chromatography.

A pH-zone-refining counter-current chromatographic method was developed for the preparative (multigram) separation and purification of components of the commercial color additive D&C Red No. 28 (phloxine B). The chromatography of 3 and 6 g of color additive yielded 1.07 and 4.06 g, respectively, of pure 2',4',5',7'-tetrabromo-4,5,6,7-tetrachlorofluorescein, the principal component of D&C Red No. 28. The importance of the quantity of retainer acid (trifluoroacetic acid) relative to the amount of salt in the color additive is discussed.

Determination of pyrrolizidine alkaloids in commercial comfrey products (Symphytum sp.).

The presence of hepatotoxic pyrrolizidine alkaloids in comfrey (Symphytum sp.) and the widespread use of decoctions of this plant as a beverage (herbal tea) are of increasing concern. A method for the extraction and solid-phase concentration and capillary gas chromatographic determination of these alkaloids and their N-oxides in botanical materials has been developed and was applied to eleven comfrey-containing products purchased from retail health-food outlets in the Washington, DC, area during May-June 1989. Nine of the 11 products were found to contain measurable quantities of one or more of the alkaloids, in ranges from 0.1 to 400.0 ppm. Products containing comfrey leaf in combination with one or more other ingredients were found to contain the lowest alkaloid levels. Highest levels were found in bulk comfrey root, followed by bulk comfrey leaf. The species of the bulk material was verified by thin-layer chromatography and other means.

Complementary use of counter-current chromatography and preparative reversed-phase high-performance liquid chromatography in the separation of a synthetic mixture of brominated tetrachlorofluoresceins.

A synthetically prepared mixture of brominated 4,5,6,7-tetrachlorofloresceins was separated by a combination of preparative reversed-phase high-performance liquid chromatography and high-speed counter-current chromatography. Two new lower-brominated subsidiary colors of D&C Red Nos. 27 and 28 (phloxine B), 4',5'-dibromo-4, 5,6,7-tetrachlorofluorescein and 2',4',5'-tribromo-4,5,6, 7-tetrachlorofluorescein, were isolated and characterized by 1H NMR and chemical ionization mass spectrometry.

Nitrosamines in rubber bands used for orthodontic purposes.

Fourteen samples from eight brands of elastic-rubber bands used in orthodontics were tested for their nitrosamine content. The presence of N-nitrosodibutylamine and N-nitrosopiperidine was confirmed. The potential for nitrosamine formation from accelerating agents used for vulcanization and from other nitrosatable amines, which may be present in rubber exposed to salivary nitrite, justifies further investigations.

Determination of benzene in polypropylene food-packaging materials and food-contact paraffin waxes.

An analytical procedure was developed for determination of benzene in polypropylene food packaging and was adapted for determination of benzene in commercial paraffin waxes intended for food-contact use. The polymer was dissolved in hexadecane at 150 degrees C. The wax was melted in an 80 degrees C oven. A simple helium-sparging apparatus was used to remove the volatile chemical from the polymer or wax. The contaminant was collected in methanol, distilled water was added, and the resulting solution was analyzed by headspace gas chromatography. The instrument was equipped with a 30 m fused silica open tubular capillary column and a photoionization detector. Average recoveries of benzene from polymer and paraffin wax at low parts-per-billion concentrations were 63 and 70%, respectively. Limits of detection and quantitation for analysis of polypropylene were 8 and 17 ppb, respectively; the limit of quantitation for analysis of paraffin wax was 2 ppb. In several commercial polypropylene products examined, benzene levels ranged from none detected to 426 ppb. In 3 commercial waxes examined, concentrations of 16-73 ppb benzene were determined. The presence of benzene was confirmed by gas chromatography/mass spectrometry.

Identification of okadaic acid from a Caribbean dinoflagellate, Prorocentrum concavum.

Lipid-soluble toxins were isolated from a Caribbean strain of the epiphytic dinoflagellate Prorocentrum concavum Fukuyo. The major lipid-soluble toxin (LD50 = 210 +/- 15 micrograms/kg i.p. in mice) was purified by normal and reversed-phase column chromatography and characterized by 1H NMR and mass spectrometry. The toxin was identified as okadaic acid by interpretation of the spectral data. Okadaic acid was previously identified as a toxic component of the related species P. lima (Ehrenberg) Dodge. The finding of okadaic acid production in P. concavum and P. lima, abundant primary producers in the ciguatera-endemic Caribbean, suggests that the role of this toxin in the etiology of ciguatera may be more significant than previously thought.

Determination and confirmation of N-nitrosodimethylamine in beer.

A qualitative method has been developed for the confirmation of N-nitrosodimethylamine (NDMA) in beer by capillary gas chromatography-mass spectrometry (GC/MS) from full mass scans after quantitation, using a gas chromatograph interfaced to a thermal energy analyzer (GC/TEA). The GC/MS method has a lower limit of confirmation of 5 ppb. In a survey of 22 imported and 42 domestic beers, NDMA was found in 60 samples by GC/TEA at levels up to 7.7 ppb, and was confirmed by GC/MS in 5 samples.

Citrus artifact interference in aflatoxin M1 determination in milk.

Dried citrus waste was fed to dairy cows, their milk was extracted, and aflatoxin M1 was quantitated by using both high pressure liquid chromatography (HPLC) and thin layer chromatography (TLC). Results indicate that a compound from the citrus waste, which is excreted into the milk, interferes with the HPLC determination of aflatoxin M1 in milk and causes a false positive test. This interference can be overcome by using TLC with proper selection of developing solvents.

Field desorption mass spectrometry of cyanogenic glycosides.

The field desorption mass spectra of several underivatized cyanogenic glycosides exhibit molecular ions or ions derived from the parent compound by protonation and alkali metal cationization. Abundant fragment ions are present and can be readily related to structure. Significant deviations from established fragmentation pathways are observed due to the nature of the aglycone. The ability to successfully determine the presence of cyanogenic glycosides by field desorption is demonstrated in crude extracts isolated from Vicia sativa, a food-contaminating plant material.

Ethchlorvynol: potential of metabolites for adverse effects in man.

Identification of low levels of a metabolite of unaltered skeletal structure, 1-chloro-3-ethynylpent-1-en-3,4-diol (VII), detected in biological specimens of both nonfatal and fatal poisonings with DL-1-chloro-3-ethylpent-1-en-4-yn-3-ol (ethchlorvynol, la), has been achieved by high-resolution GC/MS. Corroborative evidence for the assigned structure (VII) was provided by synthesis, the design of which included as a central objective, concurrent access to 1-chloro-3-ethynyl-3,4-epoxy-1-pentene (VI), the putative direct precursor of VII. The diastereomeric epoxide mixture (VI) is mutagenic toward Escherichia coli WP2 try-hcr-, a UV-deficient repair strain. By contrast, neither Ia, VI, nor VII proved to be mutagenic toward Salmonella typhimurium (TA98, TA100, TA1535, and TA1539) with or without a liver postmitochondrial fraction. However, the epoxides (VI) proved cytotoxic to, for example, TA100, which apparently overlies its potency as a mutagen. The cytotoxicity of VI was also apparent in an in vitro culture system.

GLC determination for ftorafur in biological fluids.

A GLC analysis for free ftorafur was developed to follow in drug disposition in body fluids of patients. The free drug was extracted from aqueous biological samples with chloroform, derivatized by methylation, and chromatographed on 1% HI-EFF 8BP using flame-ionization detection. The analysis is sensitive (0.25 microgram/ml of plasma) and specific for the intact molecule, and it does not interfere with subsequent fluorouracil analysis of the same sample.

Adjunct hospital emergency toxicology service. A model for a metropolitan area.

A feasibility demonstration with a gas chromatograph/mass spectrometer/computer system (GC/MS) was initiated to provide a 24-hour (seven days/week) adjunct emergency toxicology service to the hospitals in the tricounty area comprising Metropolitan Detroit. During June 1, 1974, to April 1, 1975, more than 85 different drugs and other agents were identified in the body fluids of approximately 1,000 victims of accidental or deliberate poisonings. At least one toxic substance was identified in 57% of the cases, and the presence of two or more drugs was established in one of five (19%) of the victims. This study indicates that a centrally located GC/MS/computer system can provide an effective adjunct emergency toxicology service for an entire metropolitan community and thereby provide guidelines for a prompt and rational therapy.