Frequentist and Bayesian Sample Size Determination for Single-Arm Clinical Trials Based on a Binary Response Variable: A Shiny App to Implement Exact Methods

Sample size determination typically relies on a power analysis based on a frequentist conditional approach. This latter can be seen as a particular case of the two-priors approach, which allows to build four distinct power functions to select the optimal sample size. We revise this approach when the focus is on testing a single binomial proportion. We consider exact methods and introduce a conservative criterion to account for the typical non-monotonic behavior of the power functions, when dealing with discrete data. The main purpose of this paper is to present a Shiny App providing a user-friendly, interactive tool to apply these criteria. The app also provides specific tools to elicit the analysis and the design prior distributions, which are the core of the two-priors approach.

Determination of Acidolysis Hydrocarbons in Oil/Gas Geochemical Exploration Sample By Gas Chromatograph

1 Introduction Although a mumerous of papers were reported for the chemcial or instrumental analysis of inorganic elements for the geocheical samples(Sun and Xie,2014;Sun et al.,2014;Rao et al.,2004).However,the analytical methods

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis（trimethylsily）trifluoroacetamide （BSTFA） and N-methyl-N（trimethylsily） trifluoroacetamide （MSTFA） are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone （El） and 17α-ethinylestradiol （EE2）. In this study, three trimethylsilyl （TMS） steroid derivatives, mono- and di-trimethylsilyl EE2 and mono-trimethylsilyl El, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz （TMSI） in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.

A general solution and approximation for the diffusion of gas in a spherical coal sample

The square root relationship of gas release in the early stage of desorption is widely used to provide a simple and fast estimation of the lost gas in coal mines. However, questions arise as to how the relationship was theoretically derived, what are the assumptions and applicable conditions and how large the error will be. In this paper, the analytical solutions of gas concentration and fractional gas loss for the diffusion of gas in a spherical coal sample were given with detailed mathematical derivations based on the diffusion equation. The analytical solutions were approximated in case of small values of time and the error analyses associated with the approximation were also undertaken. The results indicate that the square root relationship of gas release is the first term of the approximation, and care must be taken in using the square root relationship as a significant error might be introduced with increase in the lost time and decrease in effective diameter of a spherical coal sample.

Calorimetric Determination of Enthalpy of Formation of Natural Gas Hydrates

This paper reports the measurements of enthalpies of natural gas hydrates in typical natural gas mixture containing methane, ethane, propane and iso-butane at pressure in the vicinity of 2000 kPa (300 psi) and 6900 kPa(1000psi). The measurements were made in a multi-cell differential scanning calorimeter using modified high pressure cells. The enthalpy of water and the enthalpy of dissociation of the gas hydrate were determined from the calorimeter response during slow temperature scanning at constant pressure. The amount of gas released from the dissociation of hydrate was determined from the pumped volume of the high pressure pump. The occupation ratio (mole ratio) of the water to gas and the enthalpy of hydrate formation are subject to uncertainty of 1.5%.The results show that the enthalpy of hydrate formation and the occupation ratio are essentially independent of pressure.

A Novel Sample Introduction Technique for the Simultaneous Determination of As,Se,Ge and Hg in Chinese Medicinal Material

A novel technique of Moveable Reduction Bed Hydride Generator（MRBHG）was applied tohe hydride generation or cold vapor generation of As，Se，Ge，and Hg existing In TraditionalChinese Medicinal Material（TCM）．The simultaneous determination of the multi－elements wasperformed with ICP－MS．A solid reduction system involving the use of potassiumtetraborohydride and tartaric acid was applied to generating metal hydride or cold vaporefficiently．The factors affecting the metal cold vapor generation were studied．The mainadvantage of the technique is that only a 4μL volume of sample was required for the cold vapor

Occurrence of <i>N</i>-Acyl Homoserine Lactones in Extracts of Bacterial Strain of <i>Pseudomonas aeruginosa</i>and in Sputum Sample Evaluated by Gas Chromatography–Mass Spectrometry

This study presents a fast, accurate and sensitive technique using gas chromatography-mass spectrometry (GC-MS) for the identification and quantification of N-acyl homoserine lactones (AHLs) in the extracts of bacterial strain of Pseudomonas aeruginosa and sputum sample of a cystic fibrosis patient. This method involves direct separation and determination of AHLs by using GC-MS as simultaneous separation and characterization of AHLs were possible without any prior derivatiza-tion. Electron ionization resulted in a common fragmentation pattern with the most common fragment ion at m/z 143 and other minor peaks at 73, 57 and 43. The limit of detection for N-butanoyl, N-hexanoyl, N-octanoyl, N-decanoyl, N-dodecanoyl and N-tetradecanoyl homoserine lactones was 2.14, 3.59, 2.71, 2.10, 2.45 and 2.34 μg/L, respectively. The presence of AHLs in the culture of P. aeruginosa strain and spu-tum of a cystic fibrosis patient was achieved in selected ion monitoring (SIM) mode by using the prominent fragment at m/z 143.

Recent Development in Simultaneous Multi-Element Determination of the Platinum Group Elements and Gold in Geological and Environmental Samples

In recent years, the modern methods of multi-element analysis of precious metals have attracted wide attention in scientific research and industry. The application and development in the decomposition of samples, separation and enrichment, and modern instrumental analysis of the platinum-group elements (PGEs) and gold in geological and environmental samples have been reviewed. Finally, the tendency of analysis of precious metals is also prospected.

Determination of polychlorinated biphenyl congeners in environmental samples

A modified separation method has been developed for determinating polychlorinated biphenyl congeners in environmental samples. Direct treatment of extract with concentrated HzSO4 was employed in the first step for removal of lipids and other interfering substances, then a joint column of alumina-silica gel(Ag+) was applied to separate PCBs fraction from HCH, DDT and its analogs. After this separation, the PCBs fraction was analyzed by capillary gas chromatography with ECD detector and confirmed by GC/MS. The recoveries of individual congeners in Aroclor 1254 through the separation are about 79%-84%. The method is very efficient and useful for determination of trace amount of PCB congeners in environmental samples.

SIMULTANEOUS DETERMINATION OF EPHEDRINE AND ITS ANALOGUES IN URINE BY CAPILLARY GAS CHROMATOGRAPHY

A method is developed for the simultaneous determination of ephedrine,pseudoephedrine, norephedrine, norpseudoephedrine and methylephedrine in urine on a capillary column using nitrogen-phosphorus detector.Diphenylamine is used as the internal standard.Calibration graphs are linear down to 1.30ug/ml urine.

A Highly Sensitive and Selective Spectrofluorimetric Method for the Determination of Arsenic at Pico-Trace Levels in Some Groundwater, Real, Environmental, Biological, Food and Soil Samples Using 2-(<i>α</i>-Pyridyl)-Thioquinaldinamide

A very simple, ultra-sensitive, highly selective and non-extractive new spectrofluorimetric method for the determination of arsenic at pico-trace levels using 2-(α-pyridyl)-thioquinaldinamide (PTQA) has been developed. PTQA has been proposed as a new analytical reagent for the direct non-extractive spectrofluorimetric determination of Arsenic (V). This novel fluorimetric reagent, PTQA becomes oxidized in a slightly acidic (0.025 - 0.1 M H2SO4) solution with Arsenic (V) in absolute ethanol to produce highly fluorescent oxidized product (λex = 303 nm;λem = 365 nm). Constant and maximum fluorescence intensities were observed over a wide range of acidity (0.025 - 0.1 M H2SO4) for the period between 2 min and 24 h. Linear calibration graphs were obtained for 0.001 - 800-μgL-1 of As, having a detection limit of 0.1-ngL-1;the quantification limit of the reaction system was found to be 1-ngL-1 and the RSD was 0% - 2%. A large excess of over 60 cations, anions and complexion agents (like, chloride, phosphate, azide, tartrate, oxalate, SCN, etc.) do not interfere in the determination. The developed method was successfully used in the determination of arsenic in several Certified Reference Materials (alloys, steels, ores, human urine, hair, nails, bovine liver and sediments) as well as in some biological fluids (human blood, urine, hair, nail and milk), soil samples, food samples (vegetables, fruits, rice, corn and wheat), solutions containing both arsenic (III) and arsenic (V) speciation and complex synthetic mixtures. The results of the proposed method for assessing biological, food and soil samples were comparable with both ICP-OES & AHG-AAS and were found to be in excellent agreement.

ON-LINE ELECTROLYTIC DISSOLUTION OF SOLID METAL SAMPLE AND DETERMINATION OF COPPER IN ALLOY BY AAS

On-line dissolution of solid metal sample can be carried out by electrolysis under the control of flow injection analyzer(FIA),and the dissolved sample can be transferred to atomic spectrometer for the direct analysis.The hyphenated technique of FIA on-line electrolytic dissolution of alloy and atomic absorption spectrometer(AAS)detection is developed.The research is focused on the effects of electrolyte composition and electrolysis parameters on the sample dissolving,as well as the quantitative analysis of Cu in Al alloy samples.

Determination of Integrated Molar Absorption Coefficients for Gaseous Phenol Infrared Bands and Influence of Water Vapor on Their Values

The integrated molar absorption coefficients for ν(OH) (3655 cm-1), δ(OH) (Q branch at 1176 cm-1 or whole bands), [ν(CCring) + δ(OH)] (Q branch at 1344 cm-1 or whole bands) and γ(CH) (752 cm-1) were determined at 342 K, by recording infrared spectra of pure gaseous phenol at different partial pressure (from 0 to 33 Pa). The integrated molar absorption coefficients (ε) values were obtained with a good reproducibility and the relative uncertainty on the given values is below 2%. The influence of water on the integrated molar absorption coefficients of phenol has been investigated in a large range of nwater/nphenol values (from 0.5 to 6.1 and from 44 to 94) using distinct setups. The infrared spectra of a gas mixture containing a constant amount of phenol and different amount of water were recorded (closed cell) whereas in dynamic condition (under flow) the water partial pressure was kept constant at 1.3 kPa and the phenol partial pressure was increased from 0 to 30 Pa. It is here demonstrated that, at 342 or 355 K, the presence of water does not affect the epsilon values of δ(OH) and [ν(CCring) + δ(OH)] bands.

Determination of Perillic Acid in Bioconversion Supernatants by Gas Chromatography

Perillic acid can be obtained from microbial oxidation of the exocyclic methyl group of limonene. Due to the pharmacological potential of such a metabolite, the biotransformation processes leading to its synthesis have been approached in recent studies. A robust analytical method is needed to assess the performance of such studies. An analytical method was developed and validated to determine perillic acid in the supernatants of a yeast-induced bioconversion of limonene, involving gas chromatography (GC) and an acid-induced precipitation during the sample preparation. GC analysis was performed using a column with polyethylene glycol as stationary phase (HP-Innowax) which resulted in higher loads and better peak shape. The sample preparation involved the supernatant initial filtration and precipitation with 0.6 M HCl followed by centrifugation and dissolution in ethyl acetate. GC analysis conditions were oven from 50°C to 250°C at 20°C·min-1, and then held 5 min (total runtime 15 min). Injector was set at 280°C, and detector at 300°C. Helium was the carrier gas at 1 ml·min-1. Injections of 1.0 μl were at the split ratio 25:1. The method was validated: Linearity with R2 of 0.9992, Accuracy of 98.3% in the range 190 - 950 μg·ml-1;Limit of detection of 10.4 μg·ml-1;Repeatability of 2.1% RSD. Thus, a complete methodology to determine perillic acid in a bioconversion supernatant was developed and validated. This overall approach may be useful for bioconversions of monoterpenes by other microorganisms that metabolize limonene.

DETERMINATION OF ANTIMONY IN WATER SAMPLES BY FLOW-INJECTION HYDRIDE GENERATION ATOMIC ABSORPTION SPECTROMETRY WITH ON-LINE ION-EXCHANGE COLUMN PRECONCENTRATION

On-line ion-exchange separation and preconcentration were combined with flow-injection hydride generation atomic absorption spectrometry (HGAAS) to determine ultra-trace amounts of antimony in water samples. Antimony(Ⅲ) was preconcentrated on a micro-column packed with CPG-8Q chelating ion-exchanger using time-based sample loading and eluted by 4 mol l^(-1) HCl directly into the hydride generation AAS system. A detection limit (3σ) of 0.0015μg l^(-1) Sb(Ⅲ) was obtained on the basis of a 20 fold enrichment and with a sampling frequency of 60h^(-1). The precision was 1.0% r.s.d.(n=11) at the 0.5μg l^(-1) Sb(Ⅲ) level. Recoveries for the analysis of antimony in tap water, snow water and sea water samples were in the range 97-102%.

THE USE OF CHELATING RESIN FOR THE PRE-CONCENTRATION OF TRACE RARE EARTH ELEMENTS IN BIOLOGICAL SAMPLES AND THEIR DETERMINATION

Macroporous amino-carboxvlic chelating resin of acrylic acid series may concentrate trace rare earth in the presence of 0.1 mol/l α-hydroxy-isobutyric acid at pH 4.5.With 0.10 mol/l HCl as eluant rare earth may be eluted quantitatively and separated from Ca,Mg,Fe and Cu.This method is used to determine trace amount of rare earth in human hair,stone (in kidney and bladder),peanut,grape,strawberry,cucumber,pig liver and other biological samples.

Final Status of a Metal Sample Surface after Multipulse Laser Irradiation in an Ambient Gas

We have investigated the role of the ambient gas nature and pressure in the structure and appearance of the laser treated zone. and the influence of the total duration and temporal shape of laser pulse with the laser tight being λ= 10.6μm wavelength incident upon a metallic surface at intermediate taser intensities of 107-108 W / cm2. A plasma is accompanied by the action of the laser pulse, It acts as an active moderator among laser beam and target thus determining the final status of the contact surface

Determination of Organochlorine and Synthetic Pyrethroid Pesticide Residues in Water Samples Collected from Different Locations of Bangladesh

The present study was aimed to validate an analytical method for the quantification of 19 organochlorine and 2 synthetic pyrethroid pesticide residues in water samples using modified quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction and Gas Chromatography coupled with Electron Capture Detector (ECD). The selected pesticide residues were determined by in-house validated method. The analytical method was validated by evaluating the accuracy, precision, linearity, limit of detection (LOD) and limit of quantification (LOQ). The average recoveries of the selected pesticides ranged from 78% to 117% with RSDr ≤ 12% in two fortification levels of 0.02 and 0.1 mg/L. The linearity was ≥0.995 for all of the selected pesticides. The LOD ranged from 0.003 to 0.006 mg/L and the LOQ was 0.02 mg/L for all the selected analytes. This method was applied satisfactorily for the residue analysis of 108 water samples collected from nine districts of Bangladesh. Among the analyzed samples, only 4 had cypermethrin residues (0.026 mg/L, 0.034 mg/L, 0.045 mg/L and 0.05 mg/L). The level of detected cypermethrin residues were above the WHO recommended guide line values of water quality.

A Highly Sensitive and Selective Spectrofluorimetric Method for the Determination of Vanadium at Pico-Trace Levels in Some Real, Environmental, Biological, Soil and Food Samples Using 2-(<i>α</i>-Pyridyl)-Thioquinaldinamide

A new spectrofluorimetric reagent 2-(α-pyridyl)-thioquinaldinamide (PTQA) has been synthesized and characterized through novel reaction techniques. A very simple, ultra-sensitive and highly selective non-extractive new spectrofluorimetric method for the determination of vanadium at Pico-trace levels using 2-(α-pyridyl)-thioquinaldinamide (PTQA) has been developed. PTQA has been proposed as a new analytical reagent for the direct non-extractive spectrofluorimetric determination of vanadium (V). This novel fluorimetric reagent, PTQA becomes oxidized in a slightly acidic (0.0035 - 0.0085 M H2SO4) solution within vanadium (V) in 20% ethanol to produce highly fluorescent oxidized product (λex = 319 nm;λem = 371 nm). Constant and maximum fluorescence intensities were observed over a wide range of acidity (0.0035 - 0.0085 M H2SO4) for the period between 5 min and 24 h. Linear calibration graphs were obtained for 0.001 - 600-μg·L-1 of V, having a detection limit of 0.3-ng·L-1;the quantification limit of the reaction system was found to be 3-ng·L-1 and the RSD was 0% - 2%. A large excess of over 60 cations, anions and complexing agents (like, chloride, phosphate, azide, tartrate, oxalate, SCN- etc.) do not interfere in the determination. The developed method was successfully used in the determination of vanadium in several Certified Reference Materials (alloys, steels, serum, bovine liver, drinking water, soil and sediments) as well as in some environmental waters (potable and polluted), biological fluids (human blood, urine, hair and milk), soil samples and food samples (vegetables, rice and wheat) solutions containing both vanadium (IV) and vanadium (V) speciation and complex synthetic mixtures. The results of the proposed method for assessing biological, food and vegetable samples were comparable with inductively coupled plasma optical emission spectroscopy (ICP-OES) and atomic-absorption spectrophotometer (AAS) was found to be in excellent agreement.