Examination of 19F-NMR as a tool for investigation of drug-cyclodextrin complexes

Fluorine nuclear magnetic-resonance spectroscopy (¹⁹F-NMR) was used to measure complexation of three fluorine-containing drugs—dexamthasone, fluoxetine hydrochloride, and diflunisal sodium—with 2-hydroxypropyl-β-cyclodextrin (HPβCD). Poor aqueous solubility inhibited investigation of dexamethasone complexes with this method. Complexation caused separation of the fluorine peaks that could be assigned to the two enantiomers of fluoxetine hydrochloride. The trifluoromethyl group of the drug was not included, or only partially included, in the cyclodextrin cavity and the shift changes resulting from complexation were small (0.04 and -0.05 ppm). The NMR method, therefore, could not be used to determine complex stoichiometry and complex stability constants, as chemical-shift changes were influenced by changes in the composition of the solvent medium. The difluorophenyl group of diflunisal sodium was fully included in the cyclodextrin cavity and the chemical-shift changes were large, 2.0 and 1.4 ppm, for C2' and C4' fluorine atoms, respectively. Using the continuous variation method, a 1:1 stoichiometry was determined for the complex. The chemical shift changes could also be used to determine the stability constant (K_c) for complex formation. The value obtained for the fluorine that enters deeper into the cavity was 2000 M^-1. The data shows that, given that the drug has sufficient solubility, one-dimensional ¹⁹F-NMR can be a fast and convenient method to investigate drug-cyclodextrin complexes. However, when the results are interpreted it must be taken into account that the solvent medium can affect the chemical shifts of the fluorine peaks.     

光度比浊法测定烟草中硫酸根的含量

在丙二醇介质中,基于硫酸根离子与钡离子形成稳定的胶体沉淀,建立了光度比浊法测定烟草中硫酸根含量的分析方法。硫酸根浓度在0.0-60.0μg/mL范围内符合比耳定律,相关系数0.9992。用于测定烟草样品中的硫酸根含量,回收率范围95.8%-104.9%;变异系数1.7%(n=10)。样品测定结果与重量法基本一致,相对误差小于4.0%。方法操作简便、准确、快捷,具有实用价值。     

A sensitive chemiluminescence procedure for the determination of carbon monoxide with myoglobin-luminol chemiluminescence system

A novel chemiluminescence method combined with the flow injection technique for the determination of carbon monoxide is presented in this paper. The chemiluminescence signal based on the reaction between myoglobin and luminol in an alkaline medium was remarkably enhanced by carbon monoxide. The enhanced chemiluminescence intensity was linear with carbon monoxide concentration in the range from 0.01 to 10.0 pmol.L(-1), and the detection limit was 3x10(-3) pmol.L(-1) (3sigma). The whole process, including sampling and washing, could be completed in 0.5 min with a relative standard deviation of less than 4.0%. The proposed method was applied successfully in the assay of carbon monoxide in human serum and artificial water samples without any pretreatment procedure.     

Spectrofluorimetric determination of tin in canned foods

A simple and sensitive spectrofluorimetric method for the determination of tin as its complex with 1-(2-pyridylazo)-2-naphtol (PAN) in a mixed micellar medium was developed. The mixture of a non-ionic surfactant, Triton X-100 and an anionic surfactant, bis(2-ethylhexyl) sulfosuccinate (AOT) was used as a suitable micellar medium for solubilizing of complex and ligand and also for enhancing the fluorescence intensity of complex. In the optimum experimental conditions the maximum excitation and emission wavelengths of Sn-PAN complex were 300 and 360 nm, respectively. The calibration graph was linear in the range of 0.01-0.8 microg ml(-1) with a correlation coefficient of 0.9991. The detection limit was found to be 2 ng ml(-1). The relative standard deviation of the method for the determination of 0.1 microg ml(-1) tin was calculated to be 0.74%. The interferences caused by the presence of a number of common cations and anions were studied. Finally, the method was successfully applied to the determination of tin in various canned products.     

Determination of serum cholesterol by a modification of the isotope dilution mass spectrometric definitive method

An isotope dilution mass spectrometric (ID/MS) method for cholesterol is described that uses capillary gas chromatography with cholesterol-13C3 as the labeled internal standard. Labeled and unlabeled cholesterol are converted to the trimethylsilyl ether. Combined capillary column gas chromatography and electron impact mass spectrometry are used to obtain the abundance ratio of the unlabeled and labeled [M+.] ions from the derivative. Quantitation is achieved by measurement of each sample between measurements of two standards whose unlabeled/labeled ratios bracket that of the sample. Seven pools were analyzed by this method: standard reference material (SRM) 1951, which consists of three frozen serum pools with low, medium, and high levels of cholesterol; SRM 1952, which consists of three freeze-dried serum pools with low, medium, and high levels of cholesterol; and SRM 909, a freeze-dried serum pool. The method is a modification of our original definitive method for cholesterol. The modified method uses much better chromatographic separations to assure specificity and a new method of implementing selected ion monitoring on a magnetic mass spectrometer to obtain high-precision measurements of ion intensity ratios on narrow gas chromatographic peaks. The modified method has a coefficient of variation (CV) of 0.22%, which is an improvement over the original method's CV of 0.36%. The measurements were found to be free of interference. The high precision and absence of bias qualify this method as a candidate definitive method.     

Location of the effective diffusing-photon source in a strongly scattering medium

When a narrow laser beam illuminates a strongly scattering medium, the effective pointlike source of diffusing photons appears inside the medium. By the method worked out, which is based on measurements of the diffusive intensity of light emerging from a turbid spherical sample, the depth of this source site (the penetration depth) is determined relatively to the sample diameter, which is known accurately. By using this method of locating the effective source, we have discovered that its position inside the medium is unexpectedly deep. We obtained the penetration depth D(0) = 4.6 l* +/- 0.7 l* instead of one transport mean free path, where l* is the value of D(0) in the standard diffusion theory. Information about this source dipping is useful in diffusing-photon correlation spectroscopy because of its influence on the geometric factor calculated from the diffusion equation.     

气雾杀虫剂中氯氰菊酯的毛细管气相色谱内标法测定

氯氰菊酯属于高效、中等毒性的菊酯类农药,常用于配制卫生杀虫剂,开展简便、快速测定具有现实意义。本文设计了罐装气雾杀虫剂样品的取样方法,探讨了影响毛细管气相色谱内标法测定结果的影响因素,最佳测试条件:分流比50:1、载气流量1mL/min、氯氰菊酯与内标物质量比0.25~3.0,从而成功进行了罐装气雾杀虫剂样品定性、定量分析。氯氰菊酯4对异构体分离良好,25min出峰完毕。氯氰菊酯含量为0.245%,相对标准偏差2.2%,3个添加水平的平均回收率为101.7%~103.2%,方法的检出限为4g/L。研究结果对产品质量控制具有参考价值。     

Solvent extraction coupled on-line to a reversed micellar mediated chemiluminescence detection system for trace-level determination of atropine

A fast and sensitive method for the determination of atropine, an alkaloid closely related to cocaine, is proposed. The principles of on-line ion-pair formation of alkaloid-metal complexes and liquid-liquid extraction are applied to the chemiluminescence determination of atropine. On mixing with a reversed micellar medium of cetyltrimethylammonium chloride in dichloromethane-cyclohexane (1:1 v/v)-water (0.3 M Na2CO3) containing luminol, the ion-pair complex of tetrachloroaurate(III) with atropinium produced an analytical chemiluminescence signal when it entered the reversed micellar water pool. Using the reverse-flow injection and chemical conditions optimized for atropine in aqueous samples, a detection limit of 1 ng/mL was achieved and a linear calibration graph was obtained with a wide dynamic range from 10 ng/mL to 100 micrograms/mL. The proposed method is simple and provides a good precision with a relative standard deviation (n = 6) of ca. 3% at the atropine concentration of 100 ng/mL. After a preliminary study involving the potential interference from species of organic, inorganic, and metallic nature, the method was applied to the determination of atropine in artificial urine samples and of atropine and scopolamine in pharmaceutical formulations.     

4-(5-氯-2-吡啶)-偶氮-1,3-二氨基苯光度法测定电镀废水中的微量镍(Ⅱ)

4-(5-氯-2-吡啶)-偶氮-1,3-二氨基苯(5-Cl-PADAB)可与镍发生灵敏的显色反应,生成稳定的配位化合物。基于此建立了一种测定电镀废水中微量镍的光度法。结果表明:在2.0 mol/L HCl介质中,5-Cl-PADAB与Ni(Ⅱ)反应生成摩尔比2∶1的稳定配位化合物,其最大吸收波长为565 nm,表观摩尔吸光系数为6.42×104 L/(mol.cm),Ni(Ⅱ)含量在0～1.0 mg/L内符合比尔定律;该方法用于测定电镀废水中微量镍,结果与催化-分光光度法相符,相对标准偏差小于4.0%,加标回收率为98.5%～101.8%。     

A simple optical method for the differentiation of two types of polymeric wear debris in tissue samples

A simple low-cost optical method for differentiating two birefringent plastic materials in tissue sections is described. The method relies on the measurement of the refractive indices of the materials as standard samples, then mounting the specimen containing the mixture of materials in a medium of intermediate refractive index. The optical properties of the materials in this mounting medium permit their separate identification by use of Becke's lines. In the specific example used, ultra-high molecular weight polyethylene (UHMWPE; refractive indices 1.521 and 1.529) and polyacetal (refractive indices 1.476 and 1.492) were distinguishable from each other by mounting in sandalwood oil (refractive index 1.510). Illustrative results are given for the analysis of the comparative amounts of these two polymers in the tissues adjacent to five knee replacements obtained at revision surgery. In every case there were more UHMWPE particles than polyacetal particles.     

A modified version of the discrete ordinates method for radiative heat transfer modelling

The standard discrete ordinates method (SDOM) suffers from two major sources of inaccuracy, the ray effects and false scattering. False scattering may be significantly reduced using high order discretization schemes, while ray effects originated from abrupt changes of wall temperatures are mitigated by the modified discrete ordinates method (MDOM). However, the MDOM is insensitive to ray effects caused by sharp gradients of the emissive power of the medium. Therefore, a new version (NMDOM) is proposed to overcome this shortcoming. The accuracy of the SDOM, MDOM and NMDOM are investigated, along with the interaction between ray effects and false scattering. It is concluded that the NMDOM yields accurate solutions even for coarse spatial and angular discretizations.     

Analytical profiling of biosynthetic intermediates involved in the gentamicin pathway of Micromonospora echinospora by high-performance liquid chromatography using electrospray ionization mass spectrometric detection

In the present study, we developed a sensitive and highly selective method of detecting the biosynthetic intermediates involved in the gentamicin pathway from a cell culture of Micromonospora echinospora. A novel extraction method utilizing a dual solid-phase extraction (SPE) technique was employed to purify and recover all of the gentamicin-related components from the cell culture broth, and high-performance liquid chromatography (HPLC) coupled with electrospray ionization mass spectrometry (ESI-MS/MS) was used to analyze the extractant for gentamicin intermediates. The pH of the culture broth was adjusted to an acidic condition of pH 2 prior to the extraction. The samples were first cleaned with a reversed-phase AccuBOND C(18) cartridge, and then the aminoglycosidic components were purified using a cationic exchanger OASIS MCX cartridge. The detection limit of a gentamicin standard spiked in blank medium processed by this method was found to be approximately 5 ng for each component of the gentamicin C complex, and the mean recovery for each component of standard gentamicin was above 91% when analyzed by HPLC-ESI-MS/MS. We further demonstrated that this method enables the analytical profiling of the gentamicin-related compounds produced by wild-type M. echinospora ATCC 15835, which mainly produces the gentamicin C complex, and the UV-induced mutant strain KCTC 10506BP, which produces gentamicin B as the major product. Seven intermediates (paromamine, gentamicin A2, B, X2, A, JI-20A, and JI-20B) besides the gentamicin C complex were detected in the culture broth of both M. echinospora strains when analyzed by MS/MS for the distinct fragmentation patterns of each gentamicin component. This report displays the first example of the HPLC profiling in a wide range of structurally related biosynthetic intermediates involved in the gentamicin pathway.     

Eigensolution using lagrangian interpolation

A computationally efficient and accurate solution technique for large-order eigenvalue problems with small to medium bandwidth is presented. The algorithm—called the Sub-Polynomial Iteration (SPI) method—solves for the eigenvalues and corresponding eigenvectors. directly without any transformation to the standard form. The method is an efficient combination of several separate techniques including Sturm sequence, Lagrangian polynomial interpolation, inverse iteration with shift and Gram-Schmidt orthogonalization. Computer run times for a set of sample solution indicate the efficiency of the SPI method.     

Determination of substrate and product concentrations in lactic acid bacterial fermentations by proton NMR using the ERETIC method

A 1H NMR method is described for the determination of the concentration of a chemically diverse group of metabolites over a wide concentration range in fermentation medium. The method employs the use of the ERETIC signal, which produces a pseudo-FID acquired with the FID derived from the sample components. It is shown that this signal, once calibrated against an external standard solution, can be used to determine accurately the concentration of all components present in the medium. The method is rapid, reliable, and applicable to a wide range of biological fluids. Problems such as the invisibility of certain components in the spectrum are overcome by a simple regulation of the pH.     

A quantitative method for the determination of amphiphilic drug release kinetics from nanoparticles using a Langmuir balance

Amiodarone is a drug that is widely used in the treatment of heart disease. To circumvent side effects, colloidal drug carriers have been designed to deliver the drug specifically to the site of action. For the purposes of in vitro characterization of such particles, difficult test systems are employed that usually require the quantitative separation of the drug carrier from the release medium before analysis. In this work, a Langmuir balance was used to characterize amiodarone release. Drug-loaded nanoparticles were prepared from a biodegradable polyester and assayed for their drug release kinetics. Simultaneously, nanoparticles were analyzed for their drug release by a standard procedure based on dialysis tubes combined with high-performance, liquid chromatography. The results obtained by the Langmuir balance experiments were compared with those obtained from high-performance liquid chromatography and were found to correlate well. The interexperimental variation was 4.4% for the Langmuir method (n = 4), and the interexperimental variation for HPLC was 2.9% (n = 3). The major advantage of this new method is the possibility diminishing significantly the required sample amount for the experiment, allowing drug detection in the lower nanomolar range. Moreover, the avoidance of prior nanoparticle separation from the release medium provides important progress of this technique. The Langmuir balance has proven its adaptability as a new sensitive tool for the characterization of amphiphilic drug release kinetics.     

PC 制品中双酚 A 定量分析方法的研究

目的研究双酚A在水、乙醇(质量分数为65%,全文同)、乙酸(4%)等3种食品模拟物中的迁移行为,探讨温度对双酚A迁移行为的影响,进而建立检测聚碳酸酯(PC)制品中双酚A向食品模拟物迁移溶出的定量分析方法。方法采用溶剂萃取法提取食品模拟物中的双酚A,并用GC-MS进行迁移量测定。结果该方法的工作曲线在0.05~200 mg/L范围内线性关系良好(r=0.9997),检出限为0.02 mg/L,检测方法灵敏,精确度较高。双酚A在3种模拟液中的检出量大小顺序为乙醇(65%)水乙酸(4%)。结论双酚A在同一食品介质中的迁移量随温度的升高呈上升趋势,且向水和酒精类食品的迁移比向酸性食品的迁移显著。     

Species-specific isotope dilution-based calibration for trace element speciation and its combined uncertainty evaluation: determination of tributyltin in sediment by HPLC-ICPMS

A method is described for the determination of tributyltin (TBT) in NRCC sediment CRM PACS-2 by isotope dilution (ID) analysis using HPLC-ICPMS. Reverse spike ID analysis was performed to determine the accurate concentration of a 117Sn-enriched TBT spike using a well-characterized natural abundance TBT standard. The accuracy of the latter is critical for obtaining reliable results. A unique approach, using hydride generation GC/MS, was developed to quantify the inorganic Sn and dibutyltin impurities in the natural abundance TBT standard. The true natural abundance TBT standard concentration was obtained following correction for these impurities. The total Sn concentration in the natural abundance TBT standard was determined by ID analysis using an enriched inorganic 117Sn following closed vessel mixed-acid digestion. Calibration of the enriched inorganic 117Sn standard was achieved by reverse ID analysis against a natural abundance inorganic tin standard prepared from the high-purity metal. An overall uncertainty associated with the present method was estimated, to which the uncertainties arising from measurement of the natural abundance TBT concentration, from the measurement of the isotope ratio in the spiked sample and in the reverse ID calibration solutions, and from estimation of the extraction efficiency were the main contributors. A concentration of 1.018 +/- 0.054 mg kg(-1) (expanded uncertainty, k = 2) as tin was obtained for TBT in PACS-2 using the present method, in excellent agreement with the certified value of 0.98 +/- 0.13 mg kg(-1) (95% confidence interval). A TBT concentration of 0.97 +/- 0.11 mg kg(-1) (expanded uncertainty, k = 2) as tin in PACS-2 was determined using the standard additions technique. Much smaller expanded uncertainty was obtained with ID, clearly demonstrating its superiority in providing more accurate and precise results over the method of additions. A detection limit (3sigma) of 0.02 mg kg(-1) for TBT, based on a 0.5-g subsample, was obtained.     

Ultimate Strength Prediction of Carbon/Epoxy Tensile Specimens from Acoustic Emission Data

The objective of this paper was to predict the residual strength of post impacted carbon/epoxy composite laminates using an online acoustic emission (AE) monitoring and artificial neural networks (ANN). The laminates were made from eight-layered carbon (in woven mat form) with epoxy as the binding medium by hand lay-up technique and cured at a pressure of 100 kg/cm2 under room temperature using a 30 ton capacity compression molding machine for 24 h. 21 tensile specimens (ASTM D3039 standard) were cut from t...     

基于实测路谱的振动环境分析与模拟方法研究

目的 开展无锡市内快递运输车辆的随机振动行为分析和缓冲衬垫损伤的实验室模拟再现,旨在指导包装系统随机振动加速试验,实现包装结构科学设计。方法 实地采集无锡市内中型厢式卡车运输过程中车厢不同位置的激励振动信号与包装系统响应信号;基于实测路谱处理得到实验室等比例加速、分频段加速测试谱;最后以多层瓦楞衬垫为研究对象,分别采用标准谱、等比例加速谱、分频段加速谱进行实验室加速模拟试验,对比实地运输中瓦楞衬垫损伤情况,验证各加速模拟测试方法的损伤等效性。结果 实测路谱与标准谱在形状与量级上均存在差异;基于实测路谱的等比例加速和分频段加速模拟试验衬垫损伤率误差分别为20.2%、10.1%,远小于标准谱加速模拟测试的误差（110.1%）;相较于等比例加速试验方法,分频段加速试验试验时间缩短了19min(29.7%)。结论 验证了基于实测路谱的分频段加速模拟测试的损伤等效性与快速性,该方法对实现防护包装的精准设计具有指导意义。     

基于SYSTEM Ⅱ的新型微波中功率计量系统

SYSTEMⅡ功率传递系统是微波小功率计量领域内应用比较广泛的测试系统之一,通过对传统中功率计量方法的分析研究,提出了利用SYSTEMⅡ功率传递系统实现中功率计量的构建方案。采用低反射系数等效信号源结构,构成反射系数小、输出稳定、输出电平可调的中功率等效信号源;采用中功率衰减器和SYSTEMⅡ功率传递系统中含有的高精度终端式小功率座构成中功率传递标准,通过交替比较法,实现微波中功率计的高精度自动校准。