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1.
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
2.
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
3.
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
4.
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
5.
A number of configurations of NLi
n
Na2 (n = 1–4) species were optimized using the B3LYP–density functional theory method; the 6-31G* basis set was used in this calculation. In order to study all possible dissociation energies, some related species such as
NLi2Na, NLi
n
(n = 1–4), Li
n
(n = 1, 2) and Na
n
(n = 1, 2) were also considered. Optimizations of these species were followed by fundamental frequency calculations at the same
level. Global minima of these species were shown to adopt C
2
v
(NLi4Na2, NLi2Na2), D
3
h
(NLi3Na2) and C
s
(NLiNa2 and NLi2Na) configurations. All possible dissociation energies were obtained.
Received: 30 November 1998 / Accepted: 15 October 1999 / Published online: 14 March 2000 相似文献
6.
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
7.
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
8.
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
9.
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
10.
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
11.
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
12.
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
13.
Living cationic copolymerization of 2-isopropyl-2-oxazoline with 2-n-propyl-, 2-n-butyl-, and 2-n-nonyl-2-oxazoline results in gradient copolymers of defined composition, narrow molar mass distributions (PDI = 1.09–1.3),
and defined overall degree of polymerization, set to n = 25 for all polymers. The introduction of monomer units of stronger amphiphilic character results in a systematic decrease
of the lower critical solution temperature (LCST). The LCST modulation can be controlled by the choice of the comonomer as
well as the comonomer ratio and was tuned in the temperature range from 46 to 9 °C.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
14.
Leveriza F. Arenas Benilda S. Ebarvia Fortunato B. Sevilla III 《Analytical and bioanalytical chemistry》2010,397(7):3155-3158
A piezoelectric quartz crystal (PQC) sensor based on a molecularly imprinted polymer (MIP) has been developed for enantioselective
and quantitative analysis of d-(+)-methamphetamine (d(+)-MA). The sensor was produced by bulk polymerization and the resulting MIP was then coated on the
gold electrode of an AT-cut quartz crystal. Conditions such as volume of polymer coating, curing time, type of PQC, baseline
solvent, pH, and buffer type were found to affect the sensor response and were therefore optimized. The PQC-MIP gave a stable
response to different concentrations of d(+)-MA standard solutions (response time = 10 to 100 s) with good repeatability (RSD = 0.03
to 3.09%; n = 3), good reproducibility (RSD = 3.55%; n = 5), and good reversibility (RSD = 0.36%; n = 3). The linear range of the sensor covered five orders of magnitude of analyte concentration, ranging from 10−5 to 10−1 μg mL−1, and the limit of detection was calculated as 11.9 pg d(+)-MA mL−1
. The sensor had a highly enantioselective response to d(+)-MA compared with its response to l(−)-MA, racemic MA, and phentermine.
The developed sensor was validated by applying it to human urine samples from drug-free individuals spiked with standard d(+)-MA
and from a confirmed MA user. Use of the standard addition method (SAM) and samples spiked with d(+)-MA at levels ranging
from 1 × 10−3 to 1 × 10−2 μg mL−1 showed recovery was good (95.3 to 110.9%). 相似文献
15.
1H NMR-based metabolomics approach for exploring urinary metabolome modifications after acute and chronic physical exercise 总被引:1,自引:0,他引:1
C. Enea F. Seguin J. Petitpas-Mulliez N. Boildieu N. Boisseau N. Delpech V. Diaz M. Eugène B. Dugué 《Analytical and bioanalytical chemistry》2010,396(3):1167-1176
Metabolomics is a comprehensive method for metabolite assessment that involves measuring the overall metabolic signature of
biological samples. We used this approach to investigate biochemical changes due to acute and chronic physical exercise. Twenty-two
women using identical oral contraceptives were segregated into an untrained (n = 10) or trained (n = 12) group depending on their physical training background. The subjects performed two exercises in a randomized order:
a prolonged exercise test (75% of their
\mathop V· \textO2 max \mathop V\limits^\cdot {{\text{O}}_{2\,\;\max }} until exhaustion) and a short-term, intensive exercise test (short-term, intensive exercise anaerobic test). Urine specimens
were collected before and 30 min after each test. The samples were analyzed by 1H NMR spectroscopy, and multivariate statistical techniques were utilized to process the data. Distinguishing characteristics
were observed only in the urine profiles of specimens collected before vs. 30 min after the short-term, intensive exercise
test. The metabolites responsible for such changes were creatinine, lactate, pyruvate, alanine, β-hydroxybutyrate, acetate,
and hypoxanthine. In both groups, the excretion of lactate, pyruvate, alanine, β-hydroxybutyrate, and hypoxanthine increased
similarly after the completion of the short-term, intensive exercise test (p < 0.03). However, acetate excretion increased to a lesser extent in trained than in untrained subjects (p < 0.05). In conclusion, metabolomics is a promising tool in order to gain insight into physiological status and to clarify
the changes induced by short-term, intense physical exercise. 相似文献
16.
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
17.
18.
Evaluation of a novel ELISA for serotonin: urinary serotonin as a potential biomarker for depression
Nichkova MI Huisman H Wynveen PM Marc DT Olson KL Kellermann GH 《Analytical and bioanalytical chemistry》2012,402(4):1593-1600
Depression is a common disorder with physical and psychological manifestations often associated with low serotonin. Since
noninvasive diagnostic tools for depression are sparse, we evaluated the clinical utility of a novel ELISA for the measurement
of serotonin in urine from depressed subjects and from subjects under antidepressant therapy. We developed a competitive ELISA
for direct measurement of serotonin in derivatized urine samples. Assay performance was evaluated and applied to clinical
samples. The analytical range of the assay was from 6.7 to 425 μg serotonin/g creatinine (Cr). The limit of quantification
was 4.7 μg/g Cr. The average recovery for spiked urine samples was 104.4%. Average intra-assay variation was 4.4%, and inter-assay
variation was <20%. The serotonin analysis was very specific. No significant interferences were observed for 44 structurally
and nonstructurally related urinary substances. Very good correlation was observed between urinary serotonin levels measured
by ELISA and liquid chromatography tandem mass spectrometry (LC-MS/MS; ELISA = 1.16 × LC-MS/MS − 53.8; r = 0.965; mean % bias = 11%; n = 18). Serotonin was stable in acidified urine for 30 days at room temperature and at −20 °C. The established reference range
for serotonin was 54–366 μg/g Cr (n = 64). Serotonin levels detected in depressed patients (87.53 ± 4.89 μg/g Cr; n = 60) were significantly lower (p < 0.001) than in nondepressed subjects (153.38 ± 7.99 μg/g Cr). Urinary excretion of serotonin in depressed individuals significantly
increased after antidepressant treatment by 5-hydroxy-tryptophane and/or selective serotonin re-uptake inhibitor (p < 0.01). The present ELISA provides a convenient and robust method for monitoring urinary serotonin. It is suitable to monitor
serotonin imbalances and may be particularly helpful in evaluating antidepressant therapies. 相似文献
19.
Guardiola F Tres A Codony R Addis PB Bergmann SD Zavoral JH 《Analytical and bioanalytical chemistry》2007,389(1):277-289
A gas chromatographic method was successfully applied to determine cholesterol oxidation products (COPs) in human plasma.
The linearity, precision, recovery and sensitivity of the method were determined. Oral supplementation with a combination
of vitamin E (800 IU), C (1 g) and β-carotene (24 mg), given for 21 days to 21 patients, did not significantly decrease plasma
COP content. No correlations (n = 26) were found between initial plasma COP content and the following parameters: age, body mass index, plasma content of
α-tocopherol, cholesterol, high-density lipoprotein cholesterol and triglycerides, and fat, natural antioxidant and oxidized
lipid intake. Differences in plasma COP content between type 2 diabetic (n = 6) and nondiabetic (n = 20) patients were not statistically significant. The results from this study lead us to hypothesize that the nonenzymatic
oxidation of cholesterol in plasma is negligible compared to COPs originating from the diet. This article also includes a
comprehensive review of the drawbacks of the analytical methods of COP determination in plasma and serum. 相似文献
20.
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