Measurement of PCDDs, PCDFs, and non-ortho-PCBs by comprehensive two-dimensional gas chromatography-isotope dilution time-of-flight mass spectrometry (GC x GC-IDTOFMS)

Comprehensive two-dimensional gas chromatography with isotope-dilution time-of-flight mass spectrometry (GC × GC-IDTOFMS) was used to measure polychlorinated dibenzo-p-dioxin (PCDD), polychlorinated dibenzofuran (PCDF), and coplanar polychlorinated biphenyl (cPCB) concentrations in ash, sediment, vegetation, and fish samples. The GC × GC capability was achieved by using a quad jet, dual stage, thermal modulator. Zone compression of the GC peaks from modulation resulted in a significant increase of the signal intensity over classical GC-IDTOFMS. The GC × GC column set used an Rtx-Dioxin 2 phase as the first dimension (¹D) and an Rtx-500 as the second dimension (²D). The chromatographic separation of the 17 PCDD/Fs and the 4 cPCBs was attained in ¹D except for 2,3,7,8-TCDD and CB126 for which deconvoluted ion currents (DIC) were required to be reported separately. The Rtx-500 phase separated the bulk matrix interfering compounds from the target analytes in ²D. The instrumental limit of detection (iLODs) was 0.5 pg for 2,3,7,8-TCDD. The calibration curves showed good correlation coefficients for all the compounds investigated in the concentration range of 0.5–200 pg. GC × GC-IDTOFMS results compared favorably to those from conventional isotope-dilution one-dimensional gas chromatography-high resolution mass spectrometry (GC-IDHRMS). The comprehensive mass analysis of the TOFMS further permitted the identification of other contaminants of concern in the samples.     

Stability studies and purification procedure for nitrite solutions in view of the preparation of isotopic reference materials

The lack of reference materials, accurately certified for nitrite, is a problem in view of the importance of this species for environmental and medical reasons. This work outlines a plan for the preparation of nitrite isotopic reference materials (IRMs) in the form of high purity solutions, certified for their nitrite-nitrogen isotopic composition and nitrite concentration. To achieve the desired accuracy (expanded uncertainty U with a coverage factor k=2 of 相似文献   

The effect of pressure on hydrogen transfer reactions with quinones

The effect of pressure on the oxidation of hydroarenes 3-9 with 2,3-dichloro-5,6-dicyano-1,4-quinone (DDQ; 1 a) or o-chloranil (10), leading to the corresponding arenes, has been investigated. The activation volumes were determined from the pressure dependence of the rate constants of these reactions monitored by on-line UV/Vis spectroscopic measurements in an optical high-pressure cell (up to 3500 bar). The finding that they are highly negative and only moderately dependent on the solvent polarity (DeltaV( not equal ) = -13 to -25 in MTBE and -15 to -29 cm(3) mol(-1) in MeCN/AcOEt, 1:1) rules out the formation of ionic species in the rate-determining step and is good evidence for a hydrogen atom transfer mechanism leading to a pair of radicals in the rate-determining step, as was also suggested by kinetic measurements, studies of kinetic isotope effects, and spin-trapping experiments. The strong pressure dependence of the kinetic deuterium isotope effect for the reaction of 9,10-dihydroanthracene 5/5-9,9,10,10-D(4) with DDQ (1 a) can be attributed to a tunneling component in the hydrogen transfer. In the case of formal 1,3-dienes and enes possessing two vicinal C--H bonds, which have to be cleaved during the dehydrogenation, a pericyclic hydrogen transfer has to considered as one mechanistic alternative. The comparison of the kinetic deuterium isotope effects determined for the oxidation of tetralin 9/9-1,1,4,4-D(4)/9-2,2,3,3-D(4)/9-D(12) either with DDQ (1 a) or with thymoquinone 1 c indicates that the reaction with DDQ (1 a) proceeds in a stepwise manner through hydrogen atom transfer, analogously to the oxidations of 1,4-dihydroarenes, whereas the reaction with thymoquinone 1 c is concerted, following the course of a pericyclic hydrogen transfer. The difference in the mechanistic courses of these two reactions may be explained by the effect of the CN and Cl substituents in 1 a, which stabilize a radical intermediate better than the alkyl groups in 1 c. The mechanistic conclusions are substantiated by DFT calculations.     

One-step synthesis and characterization of difunctionalized N-confused tetraphenylporphyrins

Three disubstituted N-confused porphyrins (2-4) were prepared in ca. 4% yield using a one-pot synthesis. These porphyrins bear 3,5-di-tert-butylphenyl groups substituted at the C(5) and C(20) meso positions and para-substituted (Br, NO(2), ethynyl) phenyl groups at the C(10) and C(15) meso positions. The specific orientation of the aryl rings around the macrocycle in porphyrin 2 was definitively determined using a combination of 1D ((1)H and (13)C) and 2D (gHMQC and gHMBC) NMR spectroscopy. The absorption spectra of 2-4 in CH(2)Cl(2) and dimethylacetamide are similar to those of N-confused tetraphenylporphyrin in the same solvents but have Soret and Q-bands that are shifted to lower energies. Steady-state fluorescence measurements revealed Q(x)(0,0) and Q(x)(0,1) bands similar in energy to the unsubstituted NCPs 1i and 1e. The fluorescence quantum yield results for two of these NCPs (2, 4) are atypical of porphyrin behavior and are being further investigated by time-resolved spectroscopy.     

Hydrothermal extraction of potassium,sodium, rubidium and cesium from rocks by lithium hydroxide and determination at very low natural levels

The selective extraction of Na, K, Rb and Cs from rocks is described. The method is particularly designed for low levels of rubidium and cesium in basic and ultrabasic rocks. The rocks are decomposed with lithium hydroxide solution at 180°C. Only part of the aluminium and chromium accompany the alkali metals into solution; all other rock constitutents are left behind as insoluble lithium silicate, hydroxides of divalent metals, etc. Concentration of rubidium and cesium too low to be determined directly by flame emission spectrometry are pre-concentrated up to 25-fold by liquid-liquid extraction. Quantitative recovery (>99.5%) of the two metals is achieved by coprecipitation with potassium tetraphenylboron within the organic phase (di-isobutyl ketone) for subsequent back-extraction and dissolution in an acidic aqueous phase. Detection limits are 1 mg kg^?1 Na or K, 0.1 mg kg^?1 Rb and 0.05 mg kg^?1 Cs in the rock for the direct determination and 0.003 mg kg^?1 Rb and 0.001 mg kg^?1 Cs after preconcentration. Methods are described for the purification of lithium hydroxide and the potassium nitrate used as carrier. Results are presented for the Na₂ O, K₂O, Rb and Cs contents and the K/Rb values for 23 geochemical references samples (basic and ultrabasic rocks, and iron formation samples).     

Methyl methacrylate polymerization at samarium(II)-grafted MCM-41

Sm(II)-modified periodic mesoporous silica (PMS), Sm[N(SiHMe₂)₂]₂(THF)_x@MCM-41, was used for the synthesis of Sm(II) alkyl, alkoxide, and indenyl surface species via secondary ligand exchange. The performance of the novel Sm(II)-based organometallic–inorganic hybrid materials as initiators for the graft polymerization of methyl methacrylate (MMA) is reported. All of the Sm(II) hybrid materials including the new PMMA–PMS composites were characterized via N₂ physisorption, elemental analysis, FTIR spectroscopy, and scanning electron microscopy (SEM). The organic–inorganic composites revealed complete pore blockage as well as enrichment and strong adhesion of the polymer at the exterior of the porous silica material.     

Novel UDP-glycal derivatives as transition state analogue inhibitors of UDP-GlcNAc 2-epimerase

The "epimerisation" of UDP-GlcNAc to ManNAc, the first step in the biosynthesis of sialic acids, is catalyzed by UDP-GlcNAc 2-epimerase. In this paper we report the synthesis of transition state based inhibitors of this enzyme. To mimic the assumed first transition state of this reaction (TS 1), we designed and synthesized the novel UDP-exo-glycal derivatives 1-4. We also report herein the synthesis of 5 and 6, the first C-glycosidic derivatives of 2-acetamidoglucal, and the synthesis of the ketosides 7 and 8, which were designed as bis-substrate analogue and bis- product analogue, respectively, to mimic the second step of the reaction via the assumed second transition state TS 2.     

Crystal engineering: Supramolecular structures by cocrystallization ofMeso-1,2-diphenyl-1,2-ethanediol and bisimines,simple cases of molecular recognition

The crystal structures of molecular complexes betweenmeso- 1,2-diphenyl-1,2-ethanediol and two bisimines (N,N-(dibenzylidene)-ethylenediamine and glyoxylidene-bis(2,4-dimethyl-3-pentyl-amine) are reported at different temperatures. The structure-determining motif of the cocrystalline arrangement is one single O-H . N hydrogen bond resulting in infinite ladderlike polymers. The supramolecular structure is formed by recognition of fitting species: Thed- orl-isomers do not arrange in such structures.¹H NMR experiments show that no prearrangements take place by forming complexes in solution.     

Preliminary investigation of the application of on-line membrane extraction of trifluoroacetic acid as an aid to improvement of negative ion electrospray mass spectrometry data

We have recently investigated the biodegradation of a number of acidic aromatic compounds that give excellent chromatography using trifluoroacetic acid (TFA) based HPLC methods. Unfortunately HPLC methods using TFA are not usually compatible with detection by negative ion mass spectrometry as TFA suppresses ionisation of the analyte during the electrospray process. We present a preliminary investigation of the use of an anion-exchange micro-membrane suppressor to remove TFA on-line post column with the aim of improvement of mass spectral data using an aromatic acid as an example, Thus LC-MS using a TFA based HPLC method with negative ion mass spectral detection is shown to be possible with good sensitivity.