ELECTRODEPOSITION OP Ba－K－Bi－O AND Ba－K－M－Bi－O （M＝Rb， Pb AND La） SINGLE CRYSTALS

ＥＬＥＣＴＲＯＤＥＰＯＳＩＴＩＯＮＯＰＢａ－Ｋ－Ｂｉ－ＯＡＮＤＢａ－Ｋ－Ｍ－Ｂｉ－Ｏ（Ｍ＝Ｒｂ，ＰｂＡＮＤＬａ）ＳＩＮＧＬＥＣＲＹＳＴＡＬＳ￥ＬｉａｎｇＺｈｏｎｇＺＨＡＯ；ＪｉｎＢｉａｏＺＨＡＮＧ；ＷｅｉＨｕａＷＡＮＧＳｈｉＨｏｎｇＬＩＵ；ＤａｏＢｅ...     

SYNTHESIS OF 5－SUBSTITUTED－2－CHLORO－6－METHYL－4， 7－DIOXOBENZOTHIAZOLE DERIVATIVES

ＳＹＮＴＨＥＳＩＳ ＯＦ ５－ＳＵＢＳＴＩＴＵＴＥＤ－２－ＣＨＬＯＲＯ－６－ＭＥＴＨＹＬ－４， ７－ＤＩＯＸＯＢＥＮＺＯＴＨＩＡＺＯＬＥ ＤＥＲＩＶＡＴＩＶＥＳ￥ＣｕｉＨｕａＬＩＵ；ＢｉｎＬＵ；ＪｉｎｇＬｉｎｇＺＨＡＮＧ（Ｉｎｓｔｉｔｕｔｅｏｆｏｒｇ...     

STUDIES ON GLYCOSIDES XVII─STEREOSELECTIVE SYNTHESIS OF （2，6－DIMETIIOXY－4－ETHOXYCARBONYL） PHENYL 6－O－ACETYL－2，3，4－O－BENZYL－β－D－GLUCOPYRANOSIDE

ＳＴＵＤＩＥＳＯＮＧＬＹＣＯＳＩＤＥＳＸＶＩＩ─ＳＴＥＲＥＯＳＥＬＥＣＴＩＶＥＳＹＮＴＨＥＳＩＳＯＦ（２，６－ＤＩＭＥＴＩＩＯＸＹ－４－ＥＴＨＯＸＹＣＡＲＢＯＮＹＬ）ＰＨＥＮＹＬ６－Ｏ－ＡＣＥＴＹＬ－２，３，４－Ｏ－ＢＥＮＺＹＬ－β－Ｄ－ＧＬＵＣＯＰ...     

SYNTHESIS OF 4－（2，3－DIMETHOXY－4－ISOPROPYLBENZYL）－3－ETHOXYCARBONYLMETHYL－2－CYCLOHEXENONE

ＳＹＮＴＨＥＳＩＳ　ＯＦ　４－（２，３－ＤＩＭＥＴＨＯＸＹ－４－ＩＳＯＰＲＯＰＹＬＢＥＮＺＹＬ）－３－ＥＴＨＯＸＹＣＡＲＢＯＮＹＬＭＥＴＨＹＬ－２－ＣＹＣＬＯＨＥＸＥＮＯＮＥＳＹＮＴＨＥＳＩＳＯＦ４－（２，３－ＤＩＭＥＴＨＯＸＹ－４－ＩＳＯＰＲＯＰＹ...     

CONVERSION OF KETONES INTO1，1－DISUBSTITUTED－2，3，3－TRIFLUORO－2－PROPEN －1－OLSWITH1，1－DIBROMO－1，2，2，2－TETRLUORO ETHANE／MAGNESIUM REAGENT

ＣＯＮＶＥＲＳＩＯＮ　ＯＦ　ＫＥＴＯＮＥＳ　ＩＮＴＯ１，１－ＤＩＳＵＢＳＴＩＴＵＴＥＤ－２，３，３－ＴＲＩＦＬＵＯＲＯ－２－ＰＲＯＰＥＮ　－１－ＯＬＳＷＩＴＨ１，１－ＤＩＢＲＯＭＯ－１，２，２，２－ＴＥＴＲＬＵＯＲＯ　ＥＴＨＡＮＥ／ＭＡＧＮＥＳＩＵＭ...     

STUDIES ON THE SYNTHESIS OF SINULARIOL－D， SINULARIOL－A AND SINULARIC ACID－A．－SYNTHESIS OF （5R）－7，7－DIMETHOXY－5－［1－（2－TERT－BUTYLDIPHENYLSILOXYMETHYL）VINYL］－2－HEPTANONE

ＳＴＵＤＩＥＳＯＮＴＨＥＳＹＮＴＨＥＳＩＳＯＦＳＩＮＵＬＡＲＩＯＬ－Ｄ，ＳＩＮＵＬＡＲＩＯＬ－ＡＡＮＤＳＩＮＵＬＡＲＩＣＡＣＩＤ－Ａ．－ＳＹＮＴＨＥＳＩＳＯＦ（５Ｒ）－７，７－ＤＩＭＥＴＨＯＸＹ－５－［１－（２－ＴＥＲＴ－ＢＵＴＹＬＤＩＰＨＥＮＹＬＳ...     

STUDY ON THE SYNTHESIS， RING－OPENING REACTION AND GLYCOSIDATION OF 1，6－ANHYDRO－2，4－DI－O－BENZYL－β－D－GLUCOPYRANOSE

ＳＴＵＤＹＯＮＴＨＥＳＹＮＴＨＥＳＩＳ，ＲＩＮＧ－ＯＰＥＮＩＮＧＲＥＡＣＴＩＯＮＡＮＤＧＬＹＣＯＳＩＤＡＴＩＯＮＯＦ１，６－ＡＮＨＹＤＲＯ－２，４－ＤＩ－Ｏ－ＢＥＮＺＹＬ－β－Ｄ－ＧＬＵＣＯＰＹＲＡＮＯＳＥ￥ＨｏｎｇＬＩＡＮＧ；ＣｈａｎｇＰｅｉＦＥＩ...     

用MeSO－四（3，5－二溴－4－羟基苯基）卟啉试剂二阶导数光度法测定痕量铅

用ＭｅＳＯ－四（３，５－二溴－４－羟基苯基）卟啉试剂二阶导数光度法测定痕量铅李在均，潘教麦，徐钟隽（华东师范大学化学系，上海２０００６２）关键词：二阶导数光度法，铅的测定，人发Ｔ（ＤＢＨＰ）Ｐ是铅的高灵敏显色剂￣［１］，已用于矿样等样品中铅的测定。￣...     

THE SYNTHESIS OF 4，5－BIS（4＇－BROMOBENZYLTHIO）－1，3－DITHIOLE－2－THIONE WITH ONE DIMENSIONAL INTERMOLECULAR INTERACTIONS

ＴＨＥＳＹＮＴＨＥＳＩＳＯＦ４，５－ＢＩＳ（４＇－ＢＲＯＭＯＢＥＮＺＹＬＴＨＩＯ）－１，３－ＤＩＴＨＩＯＬＥ－２－ＴＨＩＯＮＥＷＩＴＨＯＮＥＤＩＭＥＮＳＩＯＮＡＬＩＮＴＥＲＭＯＬＥＣＵＬＡＲＩＮＴＥＲＡＣＴＩＯＮＳ￥ＦａｎｇＱＩ（Ｉｎｓｔｉｔｕｔｅｏ...     

STUDIES ON THE SYNTHESIS AND REACTIONS OF N－（1－OXO－4－CARBONYL－2，6，7－TRIOXA－1－PHOSPHABICYCLO ［2．2．2］ OCTANE）－N＇－ARYL THIOUREAS

ＳＴＵＤＩＥＳＯＮＴＨＥＳＹＮＴＨＥＳＩＳＡＮＤＲＥＡＣＴＩＯＮＳＯＦＮ－（１－ＯＸＯ－４－ＣＡＲＢＯＮＹＬ－２，６，７－ＴＲＩＯＸＡ－１－ＰＨＯＳＰＨＡＢＩＣＹＣＬＯ［２．２．２］ＯＣＴＡＮＥ）－Ｎ’－ＡＲＹＬＴＨＩＯＵＲＥＡＳＹｕＧｕｉＬＩ；Ｘｕ...     

Endonuclease-rolling circle amplification-based method for sensitive analysis of DNA-binding protein

A sensitive approach for the qualitative detection of DNA-binding protein on the microarray was developed.DNA complexes in which a partial duplex region is formed from a biotin-primer and a circle single strand DNA(ssDNA) were spotted on a microarray. The endonuclease recognition site(ERS) and the DNA-binding sites(DBS) were arranged side by side within the duplex region. The working principle of the detection system is described as follows:when the DNA-binding protein capture the DBS,the endonuclease co...     

A rapid UPLC–MS/MS method for simultaneous separation of 48 acylcarnitines in dried blood spots and plasma useful as a second-tier test for expanded newborn screening

Acylcarnitine profiling in dried blood spots (DBS) is a useful method for high-throughput newborn screening of metabolic disorders, but differentiation of isobaric and isomeric compounds is not achievable. Chromatographic methods for separation have already been reported but are specific for short-chain acylcarnitines or time-consuming. The aim of this work was to develop a fast ultraperformance liquid chromatography (UPLC)-tandem mass spectrometry (MS/MS) method for separation and quantification of a large number of acylcarnitines, including dicarboxylic acylcarnitines and hydroxyacylcarnitines, in DBS and plasma samples. Acylcarnitines from DBS and plasma were converted to their butyl esters and analyzed by electrospray ionization MS/MS. Chromatographic separation was achieved using a UPLC system equipped with an ethylene-bridged hybrid C(18) column. The correlation coefficients of the calibration curves (r(2)) ranged from 0.990 to 0.999. The limit of detection ranged from 0.002 and 0.063 μM for all compounds, and the limit of quantification ranged from 0.004 and 0.357 μM. Precision ranged from 0.8 to 8.8% and the mean recovery was 103%. Profiles of acylcarnitine isomers were investigated in specimens obtained from patients diagnosed with different inborn errors of metabolism. Acylcarnitine concentrations were also measured in 58 term newborns and compared with flow injection analysis measurements. With this newly developed UPLC-MS/MS method, the simultaneous detection of 61 (13 of these labeled) acylcarnitines in DBS and plasma can be achieved in 15 min including postrun equilibration. The method has been validated and can be used as an important component of newborn screening methods as a second-tier test for discrimination and to confirm diagnosis.     

Simple and sensitive method for spectrofluorimetric determination of dodecyl benzene sulfonic acid sodium

The interaction of poly(diallyldimethyl ammonium chloride) (PDDA) with dodecyl benzene sulfonic acid sodium (DBS) has been studied by fluorescence spectra. The fluorescence of DBS can be greatly enhanced by addition of PDDA, owing to the interaction between PDDA and DBS. The enhancement intensity of fluorescence was proportional to the concentration of DBS over the range 2.5x10(-7) to 9.6x10(-5)molL(-1). Its detection limit is 3.5x10(-7)molL(-1). The method has high sensitivity and selectivity and was applied to the determination of trace amounts of DBS in water samples with satisfactory result.     

Quantification of insulin-like growth factor-1 in dried blood spots for detection of growth hormone abuse in sport

There is significant evidence that athletes are using recombinant human growth hormone (rhGH) to enhance performance, and its use is banned by the World Anti-Doping Agency and professional sports leagues. Insulin-like growth factor-1 (IGF-1) is the primary mediator of growth hormone action and is used as a biomarker for the detection of rhGH abuse. The current biomarker-based method requires collection and expedited shipment of venous blood which is costly and may decrease the number of tests performed. Measurement of GH biomarkers in dried blood spots (DBS) would considerably simplify sample collection and shipping methods to allow testing of a greater number of samples regardless of location. A method was developed to quantify intact IGF-1 protein in DBS by liquid chromatography–tandem mass spectrometry. A step-wise acid–acetonitrile extraction was optimized to achieve a sensitive assay with a lower limit of quantification of 50 ng/mL. IGF-1 remained stable at room temperature for up to 8 days, which would allow shipment of DBS cards at ambient temperature. In a comparison between plasma concentrations of IGF-1 and concentrations measured from venous and finger prick DBS, there was good correlation and agreement, r ² of 0.8551 and accuracy of 86–113 % for venous DBS and r ² of 0.9586 and accuracy of 89–122 % for finger prick DBS. The method is intended for use as a rapid screening method for IGF-1 to be used in the biomarker method of rhGH abuse detection.     

Analysis of polyfluoroalkyl substances and bisphenol A in dried blood spots by liquid chromatography tandem mass spectrometry

Dried blood spots (DBS), collected as part of the newborn screening program (NSP) in the USA, is a valuable resource for studies on environmental chemical exposures and associated health outcomes in newborns. Nevertheless, determination of concentrations of environmental chemicals in DBS requires assays with great sensitivity, as the typical volume of blood available on a DBS with 16-mm diameter disc is approximately 50 μL. In this study, we developed a liquid–liquid extraction and high-performance liquid chromatography/tandem mass spectrometry method for the detection of perfluorooctanesulfonate (PFOS), perfluorooctanoate (PFOA), and bisphenol A (BPA) in DBS. The method was validated for accuracy, precision, and sensitivity, by spiking of target chemicals at different levels on Whatman 903 filter cards, which is used in the collection of DBS by the NSP. Contamination arising from collection, storage, and handling of DBS is an important issue to be considered in the analysis of trace levels of environmental chemicals in DBS. For the evaluation of the magnitude of background contamination, field blanks were prepared from unspotted portions of DBS filter cards collected by the NSP. The method was applied for the measurement of PFOS, PFOA, and BPA in 192 DBS specimens provided by NSP of New York State. PFOS and PFOA were detected in 100 % of the specimens analyzed. The concentrations of PFOS and PFOA measured in DBS were similar to those reported earlier in the whole blood samples of newborns. BPA was also found in 86 % of the specimens at concentrations ranging from 0.2 to 36 ng/mL (excluding two outliers). Further studies are needed to evaluate the sources of BPA exposures and health outcomes in newborns.     

Systematic parameter screening for capillary electrophoresis monitoring of surfactants on silicon wafer surfaces by designed experiments

The surface purity of silicon wafers is an important parameter to monitor for yield improvement of semiconductor devices in a production line. Surfactants are used to reduce the surface potential in order to facilitate the removal or cleaning of particles and metals. Traces of surfactant residues from the cleaning bath may still be present on the wafer surface after the final cleaning step. In this report, two capillary electrophoresis (CE) methods for the analysis of dodecylbenzene sulfonate (DBS) are developed for monitoring the surfactant residues in the wafer manufacturing process. One method is developed for the sensitive determination of all DBS homologues and isomers in one single peak. Another method is developed for the fingerprint analysis of the homologues and isomers of DBS. The Taguchi methodology was used as a systematic optimization tool for the DBS analysis by CE. The experiments were evaluated by calculating the signal-to-noise ratio values with four responses. The lowest detection limit for DBS was 15 microg/L at 95% confidence level. The percent recovery of surfactant was between 90% and 110%.     

Development and validation of a dried blood spot–HPLC assay for the determination of metronidazole in neonatal whole blood samples

A selective and sensitive high-performance liquid chromatography method with UV detection for the determination of metronidazole in dried blood spots (DBS) has been developed and validated. DBS samples [spiked or patient samples] were prepared by applying blood (30 µL) to Guthrie cards. Discs (6 mm diameter) were punched from the cards and extracted using water containing the internal standard, tinidazole. The extracted sample was chromatographed without further treatment using a reversed phase system involving a Symmetry® C18 (5 µm, 3.9?×?150 mm) preceded by a Symmetry® guard column of matching chemistry and a detection wavelength of 317 nm. The mobile phase comprised acetonitrile/0.01?M phosphate solution (KH₂PO₄), pH 4.7, 15:85, v/v, with a flow rate of 1 mL/min. The calibration was linear over the range 2.5–50 mg/mL. The limits of detection and quantification were 0.6 and 1.8 µg/mL, respectively. The method has been applied to the determination of 203 DBS samples from neonatal patients for a phamacokinetic/pharmacodynamic study.     

Development and validation of a sensitive LC‐MS/MS method for determination of tacrolimus on dried blood spots

A bioanalytical method for the quantification of tacrolimus (TAC) on dried blood spots (DBS) using liquid chromatography, electrospray ionization coupled with tandem mass spectrometry (LC‐ESI‐MS/MS) was developed and validated. It involves solvent extraction of a punch disk of DBS followed by liquid–liquid extraction. The analyte and the internal standard (IS, ascomycin) were separated on a phenyl column using an isocratic mobile phase elution at a flow rate of 0.3 mL/min. The assay was linear from 1 to 80 ng/mL. The mean recovery of TAC was 76.6%. Intra‐assay, inter‐assay imprecision and biases were all less than 15%. TAC on DBS was stable for at least 10 days at room temperature, and at least 24 h at 50°C. A chromatographic effect of the filter paper (Whatman 903) was not detected. The volume of blood (15–50 μL) and hematocrit of blood (ranging from 23.2 to 48.6%) did not show a significant influence on detection of TAC concentration by DBS‐LC‐MS/MS. Fifty samples from patients were detected by both DBS‐LC‐MS/MS and microparticle enzyme‐linked immunoassay (MEIA). TAC concentrations measured by DBS‐LC‐MS/MS method tended to be lower than those by MEIA. Copyright © 2012 John Wiley & Sons, Ltd.     

High‐performance liquid chromatographic determination of anti‐ hypertensive drugs on dried blood spots using a fluorescence detector – method development and validation

A selective and sensitive high‐performance liquid chromatography method with fluorescence detection for simultaneous determination of irbesartan, losartan and valsartan on dried blood spots (DBS) has been developed and validated. It involves solvent extraction of a punch of DBS followed by reversed‐phase liquid chromatography on a Lichrospher^® 100 RP‐18e column. Fluorescence detection was performed at 259 and 385 nm as excitation and emission wavelengths, respectively. The detection limits of irbesartan, losartan and valsartan were 1.8, 3.6 and 1.8 ng/mL respectively. The mean recoveries of irbesartan, losartan and valsartan were 98.68, 98.42 and 97.81%, respectively. The mean inter‐day and intra‐day precisions of irbesartan, losartan and valsartan were 2.07 and 1.34%, 1.42 and 1.48%, and 3.20 and 2.15% respectively. The proposed method was simple and rapid. Design of experiments was used to evaluate the robustness of the method. Copyright © 2011 John Wiley & Sons, Ltd.     

Development and validation of a mass spectrometric detection method of peginesatide in dried blood spots for sports drug testing

As recently reported, dried blood spot (DBS) analysis is an advantageous technique for doping control purposes due to the minimal invasive sample collection, the simple and economic manner, as well as the low susceptibility to manipulation. Its general applicability to the sports drug testing arena has been shown for analytes of various substance classes, all of which comprise exclusively low molecular mass compounds. The aim of the present study was to investigate whether the technique of DBS analysis is applicable also to (pegylated) peptides with relevance for doping controls. As target analyte, peginesatide (Omontys, Hematide), a recently approved pegylated erythropoietin-mimetic peptide of approximately 45 kDa, tested for the treatment of anaemia in patients with renal failure, was chosen, which has been prohibited in elite sports due to its assumed endurance enhancing effects. Therefore, a detection method for peginesatide employing DBS was developed based on extraction, proteolytic digestion and cation-exchange purification followed by liquid chromatography-tandem mass spectrometry analysis. Eventually, the assay was validated for qualitative purposes and proved to be specific, sensitive (limit of detection, 10 ng/mL) and precise (relative standard deviations below 18%), demonstrating the general suitability of DBS analysis in sports drug testing also for (pegylated) peptides.