基于氮化钛的全固态碱性pH电极的研制

p H值是溶液化学中重要的检测指标 .在工业、农业、生物、医学及环境保护等各个领域都有着广泛应用 .目前 ,多采用玻璃 p H电极进行 p H值的测量 .然而 ,玻璃 p H电极也存在一定的不足 ,玻璃敏感膜阻抗高达 1 0 10 Ω,容易造成电磁干扰 ;玻璃 p H电极极易破碎 ,难以适用于强搅拌的工业过程体系 ;氢氟酸能强烈地浸蚀玻璃膜 .因此 ,玻璃 p H电极不能长时间地用于含氟腐蚀体系 p H的测量 ;另外 ,玻璃 p H电极在强碱性溶液测量时会产生“钠差”.因此 ,多年来对非玻璃型 p H电极的研究一直是化学传感器研究领域中的活跃课题之一 .目前常见的…     

近红外光谱快速分析青贮饲料pH值和发酵产物

采用近红外光谱技术,结合偏最小二乘回归法,研究了142个不同种类的秸秆青贮饲料样品的pH值和发酵产物(乳酸、乙酸、丙酸、丁酸和氨态氮),建立了干燥粉碎和新鲜样品的近红外漫反射光谱定量分析模型以及浸提液样品的近红外透射光谱定量分析模型。研究发现,pH值的近红外漫反射光谱和透射光谱的分析效果均较好,校正模型决定系数R2和验证集样品预测值与化学值的相关关系决定系数r2都大于0.80,并且干燥粉碎、新鲜和浸提液样品的RPD值分别为3.44、2.50和2.27;3种状态样品的乳酸、乙酸、丁酸和氨态氮的定量分析模型精度需进一步提高;R2在0.64~0.85之间;RPD值在1.38~1.93之间;丙酸含量的测定结果较差。方差分析显示,3种状态样品的测定结果之间均无显著性差异(P>0.05)。     

Development and validation of a new high-performance liquid chromatography method for the determination of gliclazide and repaglinide in pharmaceutical formulations

A new high-performance liquid chromatography method was developed and validated for the quantitation of gliclazide and repaglinide in pharmaceutical formulations. Determination was performed using a LiChroCART RP-18 column, a mobile phase containing acetonitrile-phosphate buffer (pH 2.1; 60 + 40, v/v), and ultraviolet (UV) detection at 225 nm. Repaglinide was used as an internal standard for gliclazide determination and gliclazide for repaglinide assay. The method was validated with respect to linearity, precision, robustness, ruggedness, accuracy, and specificity. The calibration graphs ranged from 0.015 to 0.09 mg/mL for gliclazide and 0.06 to 0.36 mg/mL for repaglinide. Intra- and interday relative standard deviation values for the standard solutions were 0.70 and 1.01% for gliclazide and 0.78 and 0.93% for repaglinide, respectively. Total recoveries of gliclazide and repaglinide from the laboratory-prepared mixtures were 99.82 +/- 0.58 and 101.50 +/- 0.46% for gliclazide and repaglinide, respectively [mean +/- standard deviation (SD)]. In forced degradation studies, the effect of acid, base, oxidation, UV light, and temperature on both drugs was also investigated. Finally, the method was applied for the quality control of commercial gliclazide and repaglinide tablets. Total recovery was 100.40 +/- 0.35 and 104.46 +/- 0.23% for gliclazide and repaglinide, respectively (mean +/- SD).     

Potentiometric membrane sensors for the selective determination of pyridoxine hydrochloride (vitamin B6) in some pharmaceutical formulations

The construction and general performance characteristics of two novel potentiometric PVC membrane sensors responsive to the pyridoxine hydrochloride known as vitamin B6 (VB6) are described. These sensors are based on the use of the ion-association complexes of the pyridoxine cation with phosphomolybdate, and phosphotungstate counter anions as ion pair in a plasticized PVC matrix. The electrodes show a stable, near-Nernstian response for 6x10(-5)-1x10(-2) M VB6 at 25 degrees C over the pH range 2-4 with a cationic slope of 54.0+/-0.5 and 54.5+/-0.4 per concentration decade for pyridoxine-phosphomolybdate and pyridoxine-phosphotungstate respectively. The two electrodes have the same lower detection limit (4x10(-5) M) and the response times are 45-60 and 30-45 s in the same order for both. Selectivity coefficients for VB6 relative to a number of interfering substances were investigated. There is negligible interference from many cations, some vitamins and pharmaceutical excipients. Direct potentiometric determination of 15-2000 microg/ml pyridoxine shows an average recovery of 98.0% and 99.0% with relative standard deviation 1.5% and 1.2% at 100.0 microg/ml for pyridoxine-phosphomolybdate and pyridoxine-phosphotungstate electrodes, respectively. The determination of VB6 in some pharmaceutical preparations using the proposed electrodes gave an average recovery of 98.0 and 99.0% of the nominal value and a mean standard deviation of 1.1% and 0.9% (n=10) for pyridoxine-phosphomolybdate and pyridoxine-phosphotungstate electrodes, respectively. The results compare favorably with data obtained by the British Pharmacopoeia method.     

国标法测定地表水中阴离子表面活性剂方法优化

对GB/T 7494–1987测定地表水中阴离子表面活性剂含量的方法进行优化。对萃取次数、磷酸二氢钠溶液反洗以及pH调节等进行了试验研究,将萃取用的三氯甲烷总量降为25 mL,两次萃取定容后一次反洗。结果表明,萃取两次可以满足分析需求,反洗能够有效去除亚硝酸盐氮等离子干扰,中性地表水样品无需调节pH,非中性样品须调为中性后测定。方法优化后线性良好,线性相关系数大于0.999,检出限为0.012 mg/L。测定结果的相对标准偏差为0.8%~3.3%(n=6),加标回收率为92.0%~110.0%。优化后方法满足地表水分析要求,能有效降低三氯甲烷用量并简化分析步骤。     

New low-index liquid refractive index standard: SRM 1922

A new standard for the calibration of refractometers has been developed. Standard Reference Material (SRM) 1922 is a mineral oil with a refractive index nD = 1.46945 at 20 degrees C, which is within the range of the Brix scale (% sucrose). The change in refractive index with temperature (dn/dT) has been characterized for the range 15 degrees C to 35 degrees C to allow for calibrations within that range of temperatures. The refractive indices were measured at 5 wavelengths in the visible spectrum by using the method of minimum deviation with a +/- 2-3 x 10(-5) uncertainty at 20 degrees C. The values of nD and dnD/dT were determined by fits of a two-term Cauchy function to the values at the measured wavelengths with a +/- 6 x 10(-5) uncertainty in nD at 20 degrees C.     

A sensitive and selective liquid chromatographic/electrospray ionization tandem mass spectrometric assay for the simultaneous quantification of alpha-,beta-arteether and its metabolite dihydroartemisinin in plasma,useful for pharmacokinetic studies

A sensitive, selective, specific and rapid liquid chromatographic/electrospray ionization tandem mass spectrometric assay method was developed and validated for the simultaneous quantitation of alpha-,beta-arteether (alpha-,beta-AE) and its metabolite alpha-dihydroartemisinin (DHA) in monkey plasma using the propyl ether analogue of beta-arteether (PE) as an internal standard. The method involves a simple two-step liquid-liquid extraction with hexane. The analytes were chromatographed on a C(18) reversed-phase chromatographic column by isocratic elution with methanol-ammonium acetate buffer (pH 4) (92 : 8, v/v) and analysed by mass spectrometry in the multiple reaction monitoring mode. The chromatographic run time was 7 min and the weighted (1/x(2)) calibration curves were linear over the range 0.78-200 ng ml(-1). The method was validated in terms of accuracy, precision, absolute recovery, freeze-thaw stability, bench-top stability and re-injection reproducibility. The limit of detection and lower limit of quantification in monkey plasma were 0.39 and 0.78 ng ml(-1) respectively for all the analytes. The intra- and inter-batch precision and accuracy were found to be well within acceptable limits (<15%). All three analytes were stable even after three freeze-thaw cycles (deviation < 15%). The average absolute recoveries of alpha-,beta-AE, DHA and PE, used as an internal standard, from spiked plasma samples were 85.85 +/- 6.56, 70.10 +/- 7.06, 54.37 +/- 3.39 and 93.90 +/- 6.9%, respectively. The assay method described here could be applied to study the pharmacokinetics of alpha-,beta-AE and DHA in rhesus monkeys.     

UV spectrophotometric determination of bioflavonoids from a semisolid pharmaceutical dosage form containing Trichilia catigua Adr. Juss and Ptychopetalum olacoides Bentham standardized extract: analytical method validation and statistical procedures

A precise, accurate, and sensitive UV spectrophotometric method was developed and validated for routine quantification of total bioflavonoids, expressed as rutin, from a topical oil-in-water pharmaceutical emulsion containing the extract of Trichilia catigua Adr. Juss and Ptychopetalum olacoides Bentham. The method was validated experimentally, and the data were treated rigorously by statistical analysis. The following analytical parameters were assessed: linearity, specificity, intra- and interrun precision measured as relative standard deviation (RSD, %), intra- and interrun accuracy (E, %), recovery (Rec., %), limit of detection (LOD, microg/mL), and limit of quantification (LOQ, microg/mL). The UV spectrophotometric method was linear (r = 0.9995) for standard rutin over the concentration range of 5.0-15.0 microg/mL with specificity for total bioflavonoids (expressed as rutin) at 361.0 nm with an absence of interferents from the complex matrix; RSD of < or = 1.79%, intrarun (E = 97.88 +/- 1.75 to 99.0 +/- 0.33%) and interrun (E = 98.38 +/- 1.12 to 100.79 +/- 1.30%) accuracy; Rec. = 98.64 +/- 0.42 to 100.74 +/- 0.41%; LOD = 0.20 microg/mL; and LOQ = 0.30 microg/mL.     

Miniaturized membrane sensors for the determination of rivastigmine hydrogen tartrate

Novel miniaturized polyvinyl chloride (PVC) membrane sensors in all-solid state graphite and platinum wire supports were developed, electrochemically evaluated and used for the assay of rivastigmine hydrogen tartrate drug (RIV). The RIV sensors are based on the formation of an ion-association complex between the drug cation and tetrakis(4-chlorophenyl)borate (TpClPB) anionic exchanger as electroactive material dispersed in a PVC matrix. Linear responses of 10(-2) - 10(-5) M and 10(-2) - 10(-4) M with cationic slopes of 56.4 mV and 53.6 mV over the pH range 4 - 7 were obtained by using the RIV-coated graphite (sensor 1) and platinum wire (sensor 2) membrane sensors, respectively. The proposed method displays useful analytical characteristics for the determination of RIV in Exelon capsules with average recoveries of 100.01+/-0.835, 100.09+/-0.896, and in plasma with average recoveries of 99.47+/-0.97, 99.58+/-0.82, and in rat brain homogenate with average recoveries of 98.16+/-1.62, 99.02+/-1.57, for sensors 1 and 2, respectively. The methods were also used to determine the intact drug in the presence of its degradation product and thus could be used as stability indicating methods. The results obtained by the proposed procedures were statistically analyzed and compared with those obtained by using a reported method. No significant difference for both accuracy and precision was observed.     

High-resolution single-stranded DNA analysis on 4.5 cm plastic electrophoretic microchannels

Plastic microchannels (4.5 cm long) fabricated from an etched glass master were tested for high-resolution single-stranded DNA analysis. Using replaceable denaturing linear polyacrylamide as sieving matrix, one-color separation of a fragment sizing standard with single-base resolution (R > 0.5) was achieved up to 275 bases. Two-color sizing analysis of four loci short tandem repeat (STR) allelic ladder (CSF1PO, TPOX, TH01, vWA) with single-base resolution (R = 0.62) on TH01 alleles 9.3 (198 bp) and 10 (199 bp) was demonstrated. An average standard deviation of +/- 0.06 bp and +/-0.11 bp in sizing 32 alleles of the CTTv ladder was attained between runs and between channels, respectively. Four-color sequencing separation of a terminator sequencing standard showed a base-calling accuracy of 99.1% out to 320 bases in 13 min.     

分光光度法测定钻井液中示踪剂荧光素钠

研究了钻井液示踪剂荧光素钠的分光光度法测定方法。在pH9.0的乙酸钠缓冲介质中,用5cm比色皿于波长485nm条件下,分光光度法测定钻井水示踪剂荧光素钠的测量下限为0.005μg/mL。对荧光素钠含量为0.012μg/mL的水样,测量相对标准偏差(RSD)为8.7%,可以满足钻井水示踪技术要求。     

Quantitation of midazolam in human plasma by automated chip-based infusion nanoelectrospray tandem mass spectrometry

An automated chip-based infusion nanoelectrospray ionization (nanoESI) platform was used to demonstrate reproducible quantitation of drug molecules from biological matrices. Three sample preparation strategies were explored including protein precipitation of plasma with acetonitrile, de-salting of the plasma, and a combination of protein precipitation with subsequent de-salting of the dried and reconstituted extract. The best results were obtained when fortified human plasma samples containing midazolam were precipitated with acetonitrile containing alprazolam as the internal standard (IS). The supernatant was concentrated to dryness, reconstituted in aqueous acid, and de-salted by automated reversed-phase solid-phase extraction (SPE) prior to infusion nanoESI-MS/MS. Analyses employed a triple quadrupole mass spectrometer operated in selected reaction monitoring (SRM) mode. Each sample was infused for approximately 10 s and the resulting ion current profiles were integrated. Area ratios were used for regression analysis of standard samples (1.5-500 ng/mL). Quality control samples (3, 250, and 400 ng/mL) in five replicates from three different analysis days demonstrated intra-assay precision (< or =16%), inter-assay precision (< or =5%), and overall accuracy (+/-9% deviation). Infusion reproducibility of the assay was established by analyzing extracts after storage for 24 h at ambient temperature. Control plasma samples from six different sources probed the potential utility of this technique for the analysis of clinical samples. At the lower limit of quantitation (LLQ), variability and mean overall accuracy were < or =13% CV and +/-3% deviation, respectively, while at the upper limit of quantitation (ULQ) variability and mean overall accuracy were < or =9% CV and +/-9% deviation, respectively. Inter-chip variability was established by determining standard sample extracts across five different chips (< or =12% CV). Throughput for the assay was 55 s per sample, although this time may be shortened to 40 s per sample with recent improvements in the automated nanoESI system. No contamination or carryover was observed using this promising automated nanoESI-MS/MS platform.     

New highly selective picrate sensors based on charge-transfer complexes.

Two novel highly selective potentiometric membrane sensors responsive to picrate ion were developed. They are based on the use of N,N'-dibenzoyl-1,4,10,13-tetraoxa-7,16-diazacyclooctadecane (DD18C6)-picrate and Kryptofix 222-picrate charge-transfer complexes as novel electroactive materials in poly(vinyl chloride) matrix membranes plasticized with o-nitrophenyloctylether or dioctylphthalate. The sensors show a Nernstian response with anionic slopes of -59.0 +/- 0.1 and -58.0 +/- 0.2 mV decade(-1) over concentration ranges of 6.0 x 10(-5) - 1.0 x 10(-2) and 7.0 x 10(-5) - 1.0 x 10(-2) mol l(-1) picrate ion and pH ranges of 5-11.5 and 5.5-11.5 for DD18C6 and Kryptofix 222 based picrate sensors, respectively. Both sensors show highly selectivity towards picrate ion over many hydrophilic and lipophilic anions, and exhibit a non-Hofmeister selectivity sequence, which is an improvement over methods reported so far. The sensors are used for the titrimetric determination of alkaloids using picrate as a titrant.     

The use of sector field ICP-mass spectrometry for Rb-Sr geochronological dating

Rb-Sr dating, one of the most important tools in geochronology, requires determination of the Rb/Sr concentration ratios and the 87Sr/86Sr isotope ratios in co-genetic minerals or rocks and is traditionally performed by thermal ionization mass spectrometry (TIMS). In this work we investigated whether sector field inductively coupled plasma mass spectrometry (ICP-MS), which is characterized by a high sample throughput and straight-forward sample introduction, could be used as an alternative to TIMS. To avoid spectral overlap of the ion signals of the isobaric nuclides 87Sr and 87Rb, Sr was separated from Rb by cation-exchange chromatography. A mathematical correction was applied to take into account the small amount of Rb that can be present in the Sr fraction. The isotope ratio accuracy and precision attainable with ICP-MS were evaluated by analysis of several reference materials from the US Geological Survey. The results of this evaluation show that excellent accuracy could be achieved; the internal precision (repeatability) of the isotope ratio (expressed as the relative standard deviation for 10 successive 1-min measurements) was 0.04-0.12%. An attempt was made to calculate the total or combined uncertainty on the isotope ratio results, by also taking into account other possible error sources (corrections for mass discrimination, detector dead time, blank signal and Rb fraction). Finally, the same procedure was used for dating two rock formations that were 2,500 Ma and 350 Ma old, according to age determinations previously performed by the Rb-Sr laboratory of the University of München (Germany) using TIMS. The ICP-MS results (2,520 +/- 150 Ma and 379 +/- 48 Ma) obtained for these formations compare well with the corresponding TIMS data (2,509 +/- 120 Ma and 357 +/- 25 Ma).     

Trace determination of dexamethasone sodium phosphate in pharmaceutical formulations by differential pulse polarography

A simple and rapid differential pulse polarographic method has been developed for the trace determination of dexamethasone sodium phosphate. A well-defined single peak with an Ep value of -1.14 V is obtained in acetate buffer (pH 5.0). The linearity is valid in the range 0.2-1.2 mg/25 mL ( r=0.9992) with minimum detection limit of 7.6x10(-6) M. The precision of the method developed is implied from the values of relative mean deviation, standard deviation and coefficient of variation, which are 2.44%, 0.014 and 3.5% respectively. Marketed formulations of dexamethasone sodium phosphate have been analysed by calibration and standard addition methods. Recovery experiments were found to be quantitative, and analysis to determine the mass per tablet was obtained within +/-0.2% of the expected market value. The studies have shown that the method is reproducible and accurate and can be used in the analysis of marketed formulations.     

The impact of ionic strength and background electrolyte on pH measurements in metal ion adsorption experiments

Our understanding of metal ion adsorption to clay minerals has progressed significantly over the past several decades, and theories have been promulgated to describe and predict the impacts of pH, ionic strength, and background solution composition on the extent of adsorption. Studies evaluating the effects of ionic strength on adsorption typically employ a broad range of background electrolyte concentrations. Measurement of pH in these systems can be inaccurate when pH values are measured with liquid junction pH probes calibrated with standard buffers due to changes in the liquid junction potential between standard, low ionic strength (0.05 M) buffers and high ionic strength solutions (>0.1 M). The objective of this research is to determine the extent of the error in pH values measured at high ionic strength, and to develop an approach for accurately measuring pH over a range of ionic strengths using a combined pH electrode. To achieve this objective, the adsorption of cobalt (10(-5) M) onto gibbsite (10 g/L) from various electrolyte solutions (0.01-1 M) was studied. The pH measurements were determined from calibrations with standard buffers and ionic strength corrected buffer calibrations. The results show a significant effect of the aqueous solution background electrolyte anion and ionic strength on pH measurement. The 0.5 and 1 M ionic strength metal ion adsorption edges shifted to lower pH with increasing ionic strength when pH was calibrated with standard buffers whereas no shift in the adsorption edges was observed when calibrated with ionic strength corrected buffers. Therefore, to obtain an accurate pH measurement, pH calibration should contain the same electrolyte and ionic strength as the samples.     

Determination of uranium, iron, copper, and nickel in rock and water samples by MEKC

A micellar electrokinetic capillary chromatographic (MEKC) procedure has been developed for the separation and determination of dioxouranium (VI), iron(III), copper(II), and nickel(II) using bis(salicylaldehyde)propylenediimine (H2SA2Pn) as chelating reagent with a total run time of <3 min. Sodium dodecyl sulphate (SDS) was used as micellar medium at pH 8.1 with sodium tetraborate buffer (0.1 M). Uncoated fused silica capillary with effective length 38.8 cmx75 microm id was used with an applied voltage of 30 kV and photo-diode array detection at 228 nm. Linear calibrations were established within 0.045-1000 microg/mL of each element with detection limit within 15-122 ng/mL. The method was applied to the analysis of spring water and rock samples. The presence of uranium in rock and spring water samples was established within 1.58-1739.3 microg/g and 0.047-0.712 microg/mL with relative standard deviation within 0.9-2.1% and 1.3-2.6% respectively. Uranium ore and water samples were also assayed by the standard addition technique. Recovery of uranium was >98% with RSD up to 2.7%. Copper, nickel, and iron in their combined matrix were concurrently determined within RSD 0.6-3.6% (n=5) and the results obtained were compared with those of flame AAS.     

Investigation of conductometric humidity sensors

Sensors for determining humidity in air have been described and investigated. Sensing film of the devices was prepared from polyvinylalcohol and graphitized carbon black disperse phase. The composition, thermal treatment and design of sensing films were investigated and optimized. An optimized humidity sensor has better metrological parameters as compared with its prototype (response time approximately 45 s, detection limit 0.17%, slope 6.25 +/- 0.05 Theta/R.H., standard deviation of measurement 0.15%, standard deviation of analytical signal in the graduation equation 8.29Theta). Such construction of sensors have prospects in analytical practice.     

Microsized graphite sensors for potentiometric determination of cyclobenzaprine hydrochloride in pure powder, tablets, and plasma

Two cyclobenzaprine hydrochloride (CZ) microsized graphite selective sensors were investigated with dibutylsebacate as a plasticizer in a polymeric matrix of carboxylated polyvinyl chloride (PVC-COOH) in the case of sensor 1, based on the interaction between the drug and the dissociated COOH groups in the PVC-COOH. Sensor 2 was based on the interaction between the drug and ammonium reineckate, which acted as anionic electroactive material in the presence of polyvinyl chloride matrix. The two sensors were constructed by using 2-hydroxy propyl beta-cyclodextrin as an ionophore, which has a significant influence on increasing the membrane sensitivity and selectivity of both sensors. Fast and stable Nernstian responses of 1 x 10(-5) - 1 x 10(-2) and 1 x 10(-4) - 1 x 10(-2) M for the two sensors, respectively, with slopes of 58.6 and 55.5 mV/decade, respectively, over the pH range 2-4 were obtained. The proposed method displayed useful analytical characteristics for determination of CZ in its pure powder form with average recoveries 99.95 +/- 0.23 and 99.61 +/- 0.34% for sensors 1 and 2, respectively, and in plasma with good recoveries. The sensors were also used to determine the intact drug in the presence of its degradate and, thus, could be used as stability-indicating methods. The obtained results by the proposed methods were statistically analyzed and compared with those obtained by the U.S. Pharmacopeia method; no significant difference for either accuracy or precision was observed. Results obtained with the two electrodes revealed their performance characteristics, which were evaluated according to International Union of Pure and Applied Chemistry recommendations.     

Simultaneous determination of trimethyl-and triethyllead in urban dust by species-specific isotope dilution/gas chromatography-inductively coupled plasma mass spectrometry

Both (206)Pb-labeled trimethyllead (TML) and triethyllead (TEL) were synthesized from (206)Pb-enriched metallic Pb certified reference material (NIST SRM 983) and iodomethane or iodoethane through a one-process reaction in a closed system using centrifuge tubes, respectively. Organolead compounds in an urban dust reference material (BCR CRM 605) were extracted with an acetic acid/methanol (1:1) solution, which was mechanically shaken for 24 h. After adjusting the pH of the extracted solution to pH 5, the extracted organolead compounds were derivatized by tetrabutylammonium tetrabutylborate (TATB) and measured with GC-ICPMS. The analytical results of TML and TEL for BCR CRM 605 were 8.22 +/- 0.04 microg kg(-1) (mean +/- standard deviation, n = 3) and 1.12 +/- 0.06 microg kg(-1), respectively. The analytical results of TML agreed well with the certified value (7.9 +/- 1.2 microg kg(-1)).