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1.
Development of gas chromatographic method for determination of cholesterol oxides in meat products 总被引:1,自引:0,他引:1
Summary A method of extraction, purification and gas chromatographic analysis of five cholesterol oxidation products (COPs) (7β-hydroxycholesterol,
5α, 6α-epoxycholesterol, 25-hydroxycholesterol, 7-ketocholesterol and cholestane-3β, 5α, 6β-triol) has been developed. The
method is aimed at the determination of COPs in meat and meat products, in particular dry sausages, where large differences
in the content of cholesterol and its oxidation derivatives may occur. Linearity of response of trimethylsilyl ethers was
defined. The minimum concentration tested was 2.5 μg g−1 in the injected solution. The main feature of the present work is the addition of a purification step of unsaponifiables
by SPE on silica cartridges. Extraction recoveries of COP standard mixtures, performed with or without the SPE step, are evaluated.
The introduction of the clean-up step results in high purity samples without further losses in the entire process. 相似文献
2.
Lang SM Claes P Neukermans S Janssens E 《Journal of the American Society for Mass Spectrometry》2011,22(9):1508-1514
Structural information on free transition metal doped aluminum clusters, Al
n
TM
+ (TM = Ti, V, Cr), was obtained by studying their ability for argon physisorption. Systematic size (n = 5 – 35) and temperature (T = 145 – 300 K) dependent investigations reveal that bare Al
n
+ clusters are inert toward argon, while Al
n
TM
+ clusters attach one argon atom up to a critical cluster size. This size is interpreted as the geometrical transition from
surface-located dopant atoms to endohedrally doped aluminum clusters with the transition metal atom residing in an aluminum
cage. The critical size, n
crit
, is found to be surprisingly large, namely n
crit = 16 and n
crit = 19 – 21 for TM = V, Cr, and TM = Ti, respectively. Experimental cluster–argon bond dissociation energies have been derived as function of cluster size from
equilibrium mass spectra and are in the 0.1–0.3 eV range. 相似文献
3.
Sommers CD Ye H Kolinski RE Nasr M Buhse LF Al-Hakim A Keire DA 《Analytical and bioanalytical chemistry》2011,401(8):2445-2454
We evaluated polyacrylamide gel electrophoresis (PAGE) and size exclusion chromatography coupled with multi-angle laser light
scattering (SEC-MALLS) approaches to determine weight-average molecular weight (M
w) and polydispersity (PD) of heparins. A set of unfractionated heparin sodium (UFH) and low-molecular-weight heparin (LMWH) samples obtained from
nine manufacturers which supply the US market were assessed. For SEC-MALLS, we measured values for water content, refractive
index increment (dn/dc), and the second virial coefficient (A
2) for each sample prior to molecular weight assessment. For UFH, a mean ± standard deviation value for M
w of 16,773 ± 797 was observed with a range of 15,620 to 18,363 (n = 20, run in triplicate). For LMWHs by SEC-MALLS, we measured mean M
w values for dalteparin, tinzaparin, and enoxaparin of 6,717 ± 71 (n = 4), 6,670 ± 417 (n = 3), and 3,959 ± 145 (n = 3), respectively. PAGE analysis of the same UFH, dalteparin, tinzaparin, and enoxaparin samples showed values of 16,135 ± 643
(n = 20), 5,845 ± 45 (n = 4), 6,049 ± 95 (n = 3), and 4,772 ± 69 (n = 3), respectively. These orthogonal measurements are the first M
w results obtained with a large heparin sample set on product being marketed after the heparin crisis of 2008 changed the level
of scrutiny of this drug class. In this study, we compare our new data set to samples analyzed over 10 years earlier. In addition,
we found that the PAGE analysis of heparinase digested UFH and neat LMWH samples yield characteristic patterns that provide
a facile approach for identification and assessment of drug quality and uniformity. 相似文献
4.
Microwave digestion and isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-SFMS) has been applied to the
determination of Pb in rice flour. In order to achieve highly precise determination of low concentrations of Pb, the digestion
blank for Pb was reduced to 0.21 ng g−1 after optimization of the digestion conditions, in which 20 mL analysis solution was obtained after digestion of 0.5 g rice
flour. The observed value of Pb in a non-fat milk powder certified reference material (CRM), NIST SRM 1549, was 16.8 ± 0.8 ng
g−1 (mean ± expanded uncertainty, k = 2; n = 5), which agreed with the certified value of 19 ± 3 ng g−1 and indicated the effectiveness of the method. Analytical results for Pb in three brown rice flour CRMs, NIST SRM 1568a,
NIES CRM 10-a, and NIES CRM 10-b, were 7.32 ± 0.24 ng g−1 (n = 5), 1010 ± 10 ng g−1 (n = 5), and 1250 ± 20 ng g−1 (n = 5), respectively. The concentration of Pb in a candidate white rice flour reference material (RM) sample prepared by the
National Metrology Institute of Japan (NMIJ) was observed to be 4.36 ± 0.28 ng g−1 (n = 10 bottles).
Figure Digestion blank of Pb was carefully reduced to approximately 0.2 ng g-1 which permitted the highly precise determination of Pb at low ng g-1 level in foodstuff samples by ID-SFMS 相似文献
5.
Johanna Ristimaa Merja Gergov Anna Pelander Erja Halmesmäki Ilkka Ojanperä 《Analytical and bioanalytical chemistry》2010,398(2):925-935
Analysis of the major drugs of abuse in meconium has been established in clinical practice for detecting fetal exposure to
illicit drugs, particularly for the ready availability of the sample and ease of collection from diapers, compared with neonatal
hair and urine. Very little is known about the occurrence and detection possibilities of therapeutic and licit drugs in meconium.
Meconium specimens (n = 209) were collected in delivery hospitals, from infants of mothers who were suspected to be drug abusers. A targeted analysis
method by liquid chromatography–triple quadrupole mass spectrometry (LC-MS/MS) was developed for abused drugs: amphetamine,
methamphetamine, 3,4-methylenedioxyamphetamine, 3,4-methylenedioxymethamphetamine, morphine, codeine, 6-monoacetylmorphine,
oxycodone, methadone, tramadol, buprenorphine, and norbuprenorphine. A separate LC-MS/MS method was developed for 11-nor-∆9-tetrahydrocannabinol-9-carboxylic acid. A screening method based on LC coupled to time-of-flight MS was applied to a broad
spectrum of drugs. As a result, a total of 77 different compounds were found. The main drug findings in meconium were as follows:
local anesthetics 82.5% (n = 172), nicotine or its metabolites 61.5% (n = 129), opioids 48.5% (n = 101), stimulants 21.0% (n = 44), hypnotics and sedatives 19.0% (n = 40), antidepressants 18.0% (n = 38), antipsychotics 5.5% (n = 11), and cannabis 3.0% (n = 5). By revealing drugs and metabolites beyond the ordinary scope, the present procedure helps the pediatrician in cases
where maternal denial is strong but the infant seems to suffer from typical drug-withdrawal symptoms. Intrapartum drug administration
cannot be differentiated from gestational drug use by meconium analysis, which affects the interpretation of oxycodone, tramadol,
fentanyl, pethidine, and ephedrine findings. 相似文献
6.
We report the results of abundant plasma protein depletion on the analysis of underivatized N-linked glycans derived from plasma proteins by nanoLC Fourier-transform ion cyclotron resonance mass spectrometry. N-linked glycan profiles were compared between plasma samples where the six most abundant plasma proteins were depleted (n = 3) through a solid-phase immunoaffinity column and undepleted plasma samples (n = 3). Three exogenous glycan standards were spiked into all samples which allowed for normalization of the N-glycan abundances.
The abundances of 20 glycans varying in type, structure, composition, and molecular weight (1,200–3,700 Da) were compared
between the two sets of samples. Small fucosylated non-sialylated complex glycans were found to decrease in abundance in the
depleted samples (greater than or equal to tenfold) relative to the undepleted samples. Protein depletion was found to marginally
effect (less than threefold) the abundance of high mannose, hybrid, and large highly sialylated complex species. The significance
of these findings in terms of future biomarker discovery experiments via global glycan profiling is discussed. 相似文献
7.
Molecular interaction energy (MI) values calculated by molecular mechanics (MM2) using a model graphitic carbon phase were
used for studying the selectivity of different types of graphitic carbon columns. The MI values well correlated with logk values measured on a graphitic carbon synthesized from 100% organic materials (r = 0.961, n = 13) but not with logk values measured on a graphitic carbon synthesized using silica matrix (r = 0.558, n = 17). The latter logk values correlated well with the hydrogen bonding energy values calculated using a model silica phase (r = 0.856, n = 17). The reason for the poor correlation of the logk values measured on the latter graphitic carbon is that the silica matrix might not be completely eliminated in the production
process. 相似文献
8.
Mazzucchelli I Rapetti M Fattore C Franco V Gatti G Perucca E 《Analytical and bioanalytical chemistry》2011,401(3):1013-1021
The development of a simple and rapid high-performance liquid chromatography (HPLC) method for the determination of the new
antiepileptic drug rufinamide (RFN) in human plasma and saliva is reported. Samples (250 μl) are alkalinized with ammonium
hydroxide (pH 9.25) and extracted with dichloromethane using metoclopramide as internal standard. Separation is achieved with
a Spherisorb silica column (250 × 4.6 mm i.d., 5 μm) at 30 °C using as mobile phase a solution of methanol/dichloromethane/n-hexane
10/25/65 (vol/vol/vol) mixed with 6 ml ammonium hydroxide. The instrument used was a Shimadzu LC-10Av chromatograph and flow
rate was 1.5 ml min-1, with a LaChrom L-7400 UV detector set at 230 nm. Calibration curves are linear [r
2 = 0.998 ± 0.002 for plasma (n = 10) and r
2 = 0.999 ± 0.001 for saliva (n = 9)] over the range of 0.25–20.0 μg ml-1, with a limit of quantification at 0.25 μg ml-1. Precision and accuracy are within current acceptability standards. The assay is suitable for pharmacokinetic studies in
humans and for therapeutic drug monitoring. 相似文献
9.
M. Vallejo A. García J. Tuñón D. García-Martínez S. Angulo J.L. Martin-Ventura L. M. Blanco-Colio P. Almeida J. Egido C. Barbas 《Analytical and bioanalytical chemistry》2009,394(6):1517-1524
New biomarkers of cardiovascular disease are needed to augment the information obtained from traditional indicators and to
illuminate disease mechanisms. One of the approaches used in metabolomics/metabonomics for that purpose is metabolic fingerprinting
aiming to profile large numbers of chemically diverse metabolites in an essentially nonselective way. In this study, gas chromatography-mass
spectrometry was employed to evaluate the major metabolic changes in low molecular weight plasma metabolites of patients with
acute coronary syndrome (n = 9) and with stable atherosclerosis (n = 10) vs healthy subjects without significant differences in age and sex (n = 10). Reproducible differences between cases and controls were obtained with pattern recognition techniques, and metabolites
accounting for higher weight in the classification have been identified through their mass spectra. On this basis, it seems
inherently plausible that even a simple metabolite profile might be able to offer improved clinical diagnosis and prognosis,
but in addition, specific markers are being identified. 相似文献
10.
A simple and easy-to-use extraction procedure has been optimised, validated, and applied for extraction of 2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP) in urine and spiked plasma samples. PhIP is a carcinogenic and mutagenic heterocyclic aromatic amine that
is formed during cooking of meat and fish. The novelty of the extraction procedure lies in using a short piece of narrow capillary-like
microporous hollow-fibre (HF) membrane as extraction device. The HF membrane was filled with a few microlitres of acidic solution
and the membrane pores were impregnated with an organic extraction solvent. Therefore, the technique was called hollow-fibre
supported liquid membrane (HF-SLM) extraction. The HF extraction device was then supported by a syringe needle and directly
immersed in urine (1.4 mL) or plasma (0.3 mL) previously made alkaline by adding 0.5 mol L−1 NaOH solution to give a final volume of 1.6 mL. The operation of the HF-SLM extraction at the optimal conditions resulted
in a PhIP extraction efficiency of 74% from both spiked urine and plasma, corresponding to enrichment factors of 126 and 27,
respectively. For 90 min extraction time, limits of detection and quantification were, respectively, 8 and 25 pg mL−1 for urine and 6 and 11 pg mL−1 for plasma. Within-day repeatability (n = 6) and between-day reproducibility (n = 3) were, respectively, 5% and 13% for urine and 6% and 7% for plasma. Analysis of urine samples collected for 12 h after
a volunteer had eaten 250 g well-done chicken showed the PhIP concentration was 124 ± 21 pg mL−1, calculated assuming an extraction efficiency of 74%. 相似文献
11.
Gies AP Ellison ST Vergne MJ Orndorff RL Hercules DM 《Analytical and bioanalytical chemistry》2008,392(4):627-642
MALDI-TOF/TOF CID experiments are reported for hydroxylated poly(α-methylstyrene) precursor ions (PAMS: m/z 1,445.9 (n = 10), 2,036.3 (n = 15), 2,626.7 (n = 20), 3,217.1 (n = 25), and 3,807.5 (n = 30), where the number of repeat units n corresponds to the oligomer mass numbers). The influences of structure, molecular weight, and kinetic energy on degradation
mechanisms were examined to test the generality of our multi-chain fragmentation model developed for polystyrene. Our results
indicate that poly(α-methylstyrene) free radicals are formed initially through multiple chain breaks and subsequently undergo
a variety of depolymerization reactions to yield predominantly monomer and dimer species; the intensity of each species depends
on the effective kinetic energy selected for the CID process. Each depolymerization mechanism is presented in detail with
experimental and computational data to justify/rationalize the process and its kinetic energy dependence. These processes
show the complex interrelationships between the various pathways along with preferred production of tertiary radicals, which
suppresses the appearance of primary radicals. Additionally, Py-GC/MS experimental data are presented to allow a comparison
of the multimolecular free radical reactions in pyrolysis with the unimolecular fragmentation reactions of MS/MS.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
12.
Katsuhiro Inomata Reina Doi Erina Yamada Hideki Sugimoto Eiji Nakanishi 《Colloid and polymer science》2007,285(10):1129-1137
Amphiphilic polymers Cn-PHEG consisting of water-soluble poly[N
5-2-(hydroxyethyl) l-glutamine] (PHEG) and hydrophobic alkyl chain (carbon number n = 12, 14, 16, or 18) attached at the PHEG terminal was prepared, and association behavior and structure of associate for
Cn-PHEG in selective solvent (water/ethylene glycol mixed solvent) have been investigated. α-Helix content of PHEG block for
all the polymers increased with weight fraction of ethylene glycol in the mixed solvent (W
EG). By light scattering measurements, formation of a small micelle was suggested for C14-, C16-, and C18-PHEG when W
EG = 0. With the increase in W
EG, appearance of a larger associate was revealed for C16- and C18-PHEG. Evaluated molecular weight and radius of gyration suggested
that the micelle is star-like sphere when W
EG = 0 and worm-like cylinder when W
EG = 0.7. C12-PHEG did not demonstrate any distinct micellization behavior because of the weak hydrophobicity of C12 chain. 相似文献
13.
Photoelectrochemical measurements have been performed at a polybithienyl (PBT) film (doping level of 1 × 1018/cm3) deposited on a platinum electrode. The cathodic photocurrents and negative slope of the Mott-Schottky plot indicate that
the PBT film has the features of a p-type semiconductor. The cathodic photocurrents are interpreted in terms of the Gaertner-Butler
model on the basis of the theory of the semiconductor|solution interface. The (i
ph
hν)2/n vs. hν plots taken from the photocurrent spectra show two linearities for n=1 in the wavelength range from 460 nm to 490 nm and for n=4 in the wavelength range λ > 490 nm. The band gaps of the PBT film were determined to be 2.05 ± 0.05 eV for n=1 and 1.55 ± 0.05 eV for n=4. The flat-band potential is 0.33 V (vs SCE). From the slope of the Mott-Schottky plot at the modulation frequency of 3 kHz,
the dielectric constant ɛ of the film and the thickness of the depletion layer W
0 of the PBT film were determined to be 7.4 and 0.29 μm, respectively.
Received: 6 January 1999 / Accepted: 6 June 1999 相似文献
14.
The electrochemical behaviors of metol on an ionic liquid N-butylpyridinium hexafluorophosphate modified carbon paste electrode (IL-CPE) were studied in this paper. The results indicated
that a pair of well-defined quasi-reversible redox peaks of metol appeared with the decrease of overpotential and the increase
of redox peak current, which was the characteristics of electrocatalytic oxidation. The electrocatalytic mechanism was discussed
and the electrochemical parameters were calculated with results of the charge-transfer coefficient (α) as 0.45, the electrode reaction rate constant (k
s) as 4.02 × 10−3 s−1, and the diffusion coefficient (D) as 6.35 × 10−5 cm2/s. Under the optimal conditions, the anodic peak current was linear with the metol concentration in the range of 5.0 × 10−6 ∼ 1.0 × 10−3 mol/L (n = 11, γ = 0.994) and the detection limit was estimated as 2.33 × 10−6 mol/L (3σ). The proposed method was successfully applied to determination of metol content in synthetic samples and photographic solutions. 相似文献
15.
Radoi A Compagnone D Batic M Klincar J Gorton L Palleschi G 《Analytical and bioanalytical chemistry》2007,387(3):1049-1058
Bulk screen-printed electrodes (bSPEs) modified with zirconium phosphate (ZrP) and Meldola blue (MB) and by electrochemical deposition of a Reineckate film
(bMBZrPRs-SPEs) have been constructed and used as NADH sensors. Cyclic voltammetric investigation of these bulk electrochemically
modified screen-printed electrodes revealed stable catalytic activity in oxidation of the reduced form of the coenzyme nicotinamide
adenine dinucleotide (NADH). Flow-injection analysis (FIA) coupled with amperometric detection confirmed the improved stability
of the bMBZrPRs-SPEs (10−4 mol L−1 NADH, %RSD = 4.2, n = 90, pH 7.0). Other conditions, for example applied working potential (+50 mV relative to Ag|AgCl), flow rate (0.30 mL min−1) and pH-dependence (range 4.0–10.0) were evaluated and optimized. A glycerol biosensor, prepared by immobilizing glycerol
dehydrogenase (GDH) on the working electrode area of a bMBZrPRs-SPE, was also assembled. The biosensor was most stable at pH 8.5 (%RSD = 5.6, n = 70, 0.25 mmol L−1 glycerol). The detection and quantification limits were 2.8 × 10−6 and 9.4 × 10−6 mol L−1, respectively, and the linear working range was between 1.0 × 10−5 and 1.0 × 10−4 mol L−1. To assess the effect of interferences, and recovery by the probe we analyzed samples taken during fermentation of chemically
defined grape juice medium and compared the results with those obtained by HPLC. 相似文献
16.
J. Pablo Tomba Daniel Portinha Walter F. Schroeder Mitchell A. Winnik Willie Lau 《Colloid and polymer science》2009,287(3):367-378
This paper describes experiments that investigate the use of low glass transition temperature (T
g) latex particles consisting of oligomer to promote polymer diffusion in films formed from high molar mass polymer latex.
The chemical composition of both polymers was similar. Fluorescence resonance energy transfer (FRET) was used to follow the
rate of polymer diffusion for samples in which the high molar mass polymer was labeled with appropriate donor and acceptor
dyes. In these latex blends, the presence of the oligomer (with M
n = 24,000 g/mol, M
w/M
n = 2) was so effective at promoting the interdiffusion of the higher molar mass poly(butyl acrylate-co-methyl methacrylate; PBA/MMA = 1:1 by weight) polymer (with M
n = 43,00 g/mol, M
w/M
n = 3) that a significant amount of interdiffusion occurred during film drying. Additional polymer diffusion occurred during
film aging and annealing, and this effect could be described quantitatively in terms of free-volume theory.
This paper is dedicated to Professor Haruma Kawaguchi to honor his many contributions to the field of latex particles and
their applications. 相似文献
17.
A kind of erbium hexacyanoferrate (ErHCF)-modified carbon ceramic electrodes (CCEs) fabricated by mechanically attaching ErHCF
samples to the surface of CCEs derived from sol–gel technique was proposed. The resulting modified electrodes exhibit well-defined
redox responses with the formal potential of +0.215 V [vs saturated calomel electrode (SCE)] at a scan rate of 20 mV s−1 in 0.5 M KCl (pH 7) solution. The voltammetric characteristics of the ErHCF-modified CCEs were investigated by voltammetry.
Attractively, the ErHCF-modified CCEs presented good electrocatalytic activity with a marked decrease in the overvoltage about
400 mV for l-cysteine oxidation. The calibration plot for l-cysteine determination was linear at 5.0 × 10−6–1.3 × 10−4 M with a linear regression equation of I(A) = 0.558 + 0.148c (μM) (R
2 = 0.9989, n = 20), and the detection limit was 2 × 10−6 M (S/N = 3). At last, the ErHCF-modified CCEs were used for amperometric detection of l-cysteine in real samples. 相似文献
18.
Wincel H 《Journal of the American Society for Mass Spectrometry》2011,22(9):1570-1576
The thermochemical properties ΔH
o
n
, ΔS
o
n
, and ΔG
o
n
for the hydration of sodiated and potassiated monosaccharides (Ara = arabinose, Xyl = xylose, Rib = ribose, Glc = glucose,
and Gal = galactose) have been experimentally studied in the gas phase at 10 mbar by equilibria measurements using an electrospray
high-pressure mass spectrometer equipped with a pulsed ion beam reaction chamber. The hydration enthalpies for sodiated complexes
were found to be between −46.4 and −57.7 kJ/mol for the first, and −42.7 and −52.3 kJ/mol for the second water molecule. For
potassiated complexes, the water binding enthalpies were similar for all studied systems and varied between −48.5 and −52.7
kJ/mol. The thermochemical values for each system correspond to a mixture of the α and β anomeric forms of monosaccharide
structures involved in their cationized complexes. 相似文献
19.
Functional surfaces and especially the control of surface properties depending on external parameters such as light illumination
have gained increasing importance in the last few years. We present the characterization of polymers from the cycloolefin
(co)polymer class (COC/COP) functionalized with an aminosilane as a basis for the further immobilization of compounds. In
a first step, an assay using AlexaFluor?647 fluorescent dye was used to assess surface homogeneity and reproducibility. A
coefficient of variation of less than 15% for dot-to-dot and less than 25% for chip-to-chip could be achieved. The same amino-functionalized
surfaces were then used to immobilize a biotinylated photolabile linker compound, binding AlexaFluor?647-labeled streptavidin.
The linker was photocleaved with high efficiency at λ = 365 nm and P = 0.15 mW/cm2. Fluorescence measurements show that polymers of the COC/COP class can be used as versatile surfaces for the photoinduced
release of compounds immobilized via photolabile linkers. 相似文献
20.
Carbohydrazide is prepared by reacting dimethyl carbonate with hydrazine hydrate. Its single crystal has been cultured with slow evaporation method. Its molecular structure and crystal structure have been determined by X-ray single crystal diffraction technique. The obtained results shows that the crystal belongs to Crystal system of Monoclinic, space group P2(1)/n with crystal parameters of a = 3.725(1), b = 8.834(2), c = 11.96(3), β = 91.97(1)°, V = 392.23(2) 3, Z = 4, D
c = 1.522 g/cm3, μ = 0.128 mm−1, F0 0 0) = 192. Based on the crystal data, we have also carried quantum chemistry calculations on the title compound using the B3LYP and MP2 method with cc-pVTZ basis set. The calculation results further demonstrate the molecular structure of title compound and its coordination properties. 相似文献