Tensile testing of freestanding polymer thin films with non-standard geometries

While an increasing requirement from both fundamental and application, a direct tensile testing of freestanding polymer thin films in the air remains a challenge, mainly due to their extreme fragility. This study aims to establish a facile and reliable testing system, and investigate the effect of specimen geometry on the testing. First, a thin film transfer and adhesive guide frame gripping technique is introduced. With low length-to-width ratio specimens, tensile testing of rectangle non-standard polystyrene films with thickness down to 45 nm is achieved on a commercial universal testing machine. By changing specimen width and gauge length individually, a scale law between system compliance and specimen width is then verified. After corrected by compliance, a constant modulus of ~3.15 GPa for 45–4319 nm thick polystyrene films can be obtained. This study provides a potential strategy to overcome operational difficulties in performing tensile testing of freestanding polymer thin films.     

Probabilistic uncertainty estimator for gamma-spectroscopy measurements

To properly interpret the quality of a gamma-spectroscopy measurement, an uncertainty estimate must be made. The uncertainty in the efficiency calibration is the dominant component to the total propagated measurement uncertainty for many types of measurements. Any deviations between the as-calibrated geometry and the as-measured geometry contribute to the total uncertainty. A mathematical technique has been developed to evaluate the variations between calibration and measurement conditions. A sensitivity analysis mode identifies those variables with the largest contribution to the uncertainty. The uncertainty mode uses probabilistic techniques for the combined variables to compute average efficiency and uncertainty, and then to propagate those values with the gamma-spectroscopic analysis into the final result for that sample.     

Activation analysis with a high-resolution high rate gamma-spectroscopy system

A high-resolution high-rate ψ-spectroscopy system is essential or, respectively, useful in three groups of applications: (1) measurement of nuclides with half-lives of less than one second; (2) Measurement of nuclides with half-lives in the second range at high sample activity; (3) Measurement in the same counting geometry of sample series of highly different sample activities. Examples are given for these applications.     

Quantitative analysis of slurry sample by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been employed for the analysis of slurry samples. Quantitative analysis of slurry samples is crucial and challenging. The problems associated with slurry samples include splashing, surface turbulence, and the difficulties of obtaining reproducible samples due to sedimentation. The LIBS analysis has achieved limited success due to inherent disadvantages when applied to slurry samples. In order to achieve improved measurement precision and accuracy, a spin-on-glass sampling method was evaluated. Five elements (Al, Ca, Fe, Ni, and Si) were examined in five slurry simulants containing varying amounts of each ion. Three calibration models were developed by using univariate calibration, multiple linear regression, and partial least square regression. LIBS analysis results obtained from the partial least square regression model were determined to be the best fit to results obtained from inductively coupled plasma optical emission spectroscopy analysis.     

便携式X射线荧光光谱法结合支持向量回归算法定量分析土壤中的砷含量

研究了基于统计学习理论的支持向量机（SVM）回归法在X射线荧光光谱定量分析中的应用。以39个农田土壤样品作为实验材料,以其中32个土壤样品作为校正集,选用SVM模型中Linear、Poly和RBF 3种核函数对As元素含量与荧光光谱数据进行回归建模。用3种不同模型对预测集中7个土壤样品的As元素含量进行预测分析,结果显示模型预测As元素含量与电感耦合等离子体发射光谱法测定的As元素含量之间的相关系数R2均大于0.99,相对分析误差RPD均大于3,表明所建立的SVM模型具有较好的使用价值。为了进一步考察SVM回归模型的预测效果,同应用较成熟的PLS回归模型的预测结果进行对比,结果显示SVM法的预测结果更好,表明SVM回归模型亦可用于便携式X射线荧光光谱法的定量预测分析。     

Quantitative headspace analysis of solid samples; a classification of various sample types

Summary Volatile compounds in various solid samples have been analyzed quantitatively by equilibrium headspace gas chromatography with the technique of multiple headspace extraction (MHE). Solid samples can represent either a partition system, such as certain polymers, or an adsorption system, particularly when present as porous material. It has been found that the humidity of the sample has a strong influence on the equilibration in an adsorption system with a hydrophilic matrix and that the addition of water increases the volatility and speeds up the equilibration time. The influence of various important parameters, such as temperature, time, size and structure of the solid samples on the equilibration is demonstrated on the examples of the quantitative determination of vinyl chloride monomer in PVC, styrene in polystyrene, ethylene in polyethylene, ethylene oxide in a contact lens, halogenated hydrocarbons in coffee and residual solvents in drugs. Presented at the 15th International Symposium on Chromatography, Nürnberg, October 1984     

Immuno-based sample preparation for trace analysis

Immuno-based sample preparation techniques are based upon molecular recognition. Thanks to the high affinity and high selectivity of the antigen–antibody interaction, they have been shown to be a unique tool in the sampling area. Immuno-based sample preparation methods include the widely encountered immunoaffinity extraction sorbents, so-called immunosorbents, as well as membrane-based or ultrafiltration techniques. This review describes the new developments and applications that have occurred in recent years with emphasis on (i) the antigen–antibody interactions, (ii) and their importance for the properties and use of immunosorbents, (iii) multiresidue extractions, (iv) the on-line coupling to chromatographic or electrophoretic separations, and (v) the high potential for improving MS detection. The recent use of artificial antibodies for sample pretreatment, so-called molecularly imprinted polymers, is also described.     

Urine sample preparation for proteomic analysis

Sample preparation for both environmental and more importantly biological matrices is a bottleneck of all kinds of analytical processes. In the case of proteomic analysis this element is even more important due to the amount of cross‐reactions that should be taken into consideration. The incorporation of new post‐translational modifications, protein hydrolysis, or even its degradation is possible as side effects of proteins sample processing. If protocols are evaluated appropriately, then identification of such proteins does not bring difficulties. However, if structural changes are provided without sufficient attention then protein sequence coverage will be reduced or even identification of such proteins could be impossible. This review summarizes obstacles and achievements in protein sample preparation of urine for proteome analysis using different tools for mass spectrometry analysis. The main aim is to present comprehensively the idea of urine application as a valuable matrix. This article is dedicated to sample preparation and application of urine mainly in novel cancer biomarkers discovery.     

Quantitative HPLC-MS analysis of nucleotide sugars in plant cells following off-line SPE sample preparation

An analytical workflow was developed for the absolute quantification of uridine diphosphate (UDP)-sugars in plant material in order to compare their metabolism both in wild-type Arabidopsis thaliana and mutated plants (ugd2,3) possessing genetic alterations within the UDP-glucose dehydrogenase genes involved in UDP-sugar metabolism. UDP-sugars were extracted from fresh plant material by chloroform-methanol-water extraction and further purified by solid-phase extraction with a porous graphitic carbon adsorbent with extraction efficiencies between 80?±?5 % and 90?±?5 %. Quantitative determination of the UDP-sugars was accomplished through HPLC separation with a porous graphitic carbon column (Hypercarb^TM) which was interfaced to electrospray ionization Orbitrap mass spectrometry. The problem of instable retention times due to redox processes on the stationary phase were circumvented by grounding of the column effluent and incorporation of a column regeneration procedure using acetonitrile-water containing 0.10 % trifluoroacetic acid. The method was calibrated using external calibration and UDP as internal standard. Calibration functions were approximated by first- or second-order regression analysis for concentrations spanning three orders of magnitude. Upon injecting sample volumes of 2.65 μL, the limits of detection for the UDP-sugars were in the 70 nmol L^?1 range. Six different UDP-sugars, including UDP-glucose, UDP-galactose, UDP-arabinose, UDP-xylose, UDP-glucuronic acid, and UDP-galacturonic acid were found in concentrations of 0.4 to 38 μg/g plant material. Data evaluation by analysis of variance (ANOVA) revealed statistically significant differences in UDP-sugar concentrations between wild-type and mutant plants, which were found to conclusively mirror the impaired metabolic pathways in the mutant plants.

Setup for evaluation of fatigue crack growth in rubber: Pure shear sample geometries tested in tension-compression mode

A novel measurement setup is developed to determine fatigue crack growth and heat build-up in rubber. Loading conditions include tensile and compressional loads. Deviations in the crack shape are detected with special features (swivel arm and additional light sources) and provide the possibility of a subsequent manual correction of the shadow crack length. This results in improved reproducibility and a worst-case scenario is obtained.     

Application of XRF and field portable XRF for environmental analysis

The aim of the present review is to evaluate, on the basis of published papers, the real potential of XRF technique for environmental analysis. Special attention is given for the determination of heavy metal pollution in water. Results of numerous papers for various samples are presented. Some details of the technique and preconcentration methods employed are also discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Next generation planar waveguide detection of microcystins in freshwater and cyanobacterial extracts,utilising a novel lysis method for portable sample preparation and analysis

The study details the development of a fully validated, rapid and portable sensor based method for the on-site analysis of microcystins in freshwater samples. The process employs a novel lysis method for the mechanical lysis of cyanobacterial cells, with glass beads and a handheld frother in only 10 min. The assay utilises an innovative planar waveguide device that, via an evanescent wave excites fluorescent probes, for amplification of signal in a competitive immunoassay, using an anti-microcystin monoclonal with cross-reactivity against the most common, and toxic variants. Validation of the assay showed the limit of detection (LOD) to be 0.78 ng mL⁻¹ and the CCβ to be 1 ng mL⁻¹. Robustness of the assay was demonstrated by intra- and inter-assay testing. Intra-assay analysis had % C.V.s between 8 and 26% and recoveries between 73 and 101%, with inter-assay analysis demonstrating % C.V.s between 5 and 14% and recoveries between 78 and 91%. Comparison with LC–MS/MS showed a high correlation (R² = 0.9954) between the calculated concentrations of 5 different Microcystis aeruginosa cultures for total microcystin content. Total microcystin content was ascertained by the individual measurement of free and cell-bound microcystins. Free microcystins can be measured to 1 ng mL⁻¹, and with a 10-fold concentration step in the intracellular microcystin protocol (which brings the sample within the range of the calibration curve), intracellular pools may be determined to 0.1 ng mL⁻¹. This allows the determination of microcystins at and below the World Health Organisation (WHO) guideline value of 1 μg L⁻¹. This sensor represents a major advancement in portable analysis capabilities and has the potential for numerous other applications.     

Microfluidic Wheatstone bridge for rapid sample analysis

We developed a microfluidic analogue of the classic Wheatstone bridge circuit for automated, real-time sampling of solutions in a flow-through device format. We demonstrate precise control of flow rate and flow direction in the "bridge" microchannel using an on-chip membrane valve, which functions as an integrated "variable resistor". We implement an automated feedback control mechanism in order to dynamically adjust valve opening, thereby manipulating the pressure drop across the bridge and precisely controlling fluid flow in the bridge channel. At a critical valve opening, the flow in the bridge channel can be completely stopped by balancing the flow resistances in the Wheatstone bridge device, which facilitates rapid, on-demand fluid sampling in the bridge channel. In this article, we present the underlying mechanism for device operation and report key design parameters that determine device performance. Overall, the microfluidic Wheatstone bridge represents a new and versatile method for on-chip flow control and sample manipulation.     

Miniaturization in sample treatment for environmental analysis

The increasing demand for faster, more cost-effective and environmentally friendly analytical methods is a major incentive to improve the classical procedures used for sample treatment in environmental analysis. In most classical procedures, the use of rapid and powerful instrumental techniques for the final separation and detection of the analytes contrasts with the time-consuming and usually manual methods used for sample preparation, which slows down the total analytical process. The efforts made in this field in the past ten years have led to the adaptation of existing methods and the development of new techniques to save time and chemicals, and improve overall performance. One route has been to develop at-line or on-line and, frequently, automated systems. In these approaches, miniaturization has been a key factor in designing integrated analytical systems to provide higher sample throughput and/or unattended operation. Selected examples of novel developments in the field of miniaturized sample preparation for environmental analysis are used to evaluate the merits of the various techniques on the basis of published data on real-life analyses of trace-level organic pollutants. Perspectives and trends are briefly discussed.     

Hand-held syringe as a portable plastic pump for on-chip continuous-flow PCR: miniaturization of sample injection device

On-chip continuous-flow polymerase chain reactions (PCRs) generally require peripheral apparatus such as a pump for injecting a sample liquid into the fluidic channel. This makes the overall instrumentation bulky, limiting integration. In this study, we propose a new scheme for injecting a sample employing a hand-held syringe as a portable plastic pump, and apply it to an on-chip continuous-flow PCR. In the proposed injection scheme, sample actuation was realized inside a highly gas-permeable and blunt-ended fluidic conduit connected to a hand-held plastic syringe filled with compressed air. In this system, the degree of air diffusion via the walls of the gas-permeable conduit becomes greater in the anterior (closer to the outlet) end of the sample plug than the posterior (closer to the inlet) end, because a relatively larger quantity of air is retained inside the syringe at the posterior end of the sample plug. This creates a pressure gradient at the inlet and outlet of the fluidic conduit and propels the sample forward toward the outlet. Preliminary experiments were performed for the quantitative analyses and evaluation of the proposed sample injection scheme using gas-permeable silicone tubes. As practical applications, a 230 bp gene fragment from a plasmid vector and the first 282 bp of the interferon-beta (IFN-β) promoter from a human genomic DNA were successfully amplified on a microdevice coupled with a hand-held syringe as a portable sample actuation device, greatly enhancing device portability for on-site analyses.     

A proposed k0 based methodology for neutron activation analysis of samples of non-standard geometry

An internal mono-standard method has been proposed for multi element analysis. This method gives the relative concentration of the elements in a sample of non-standard shape and size. It utilizes an in-situ relative efficiency calibration and hence, does not need the cumbersome procedures, otherwise required to correct for -attenuation in the sample. To validate this method, the relative concentration of elements in IAEA RM's SL-3 and Soil-7 were analyzed with sample amounts ranging from a few milligrams to grams. The samples were counted in different non-specific geometries. The results are in good agreement with the recommended values, suggesting that this methodology could be applied for the analysis of samples of non-standard size and shape, and in principle, for the analysis of large samples.     

Quantitative and qualitative measure of intralaboratory two-dimensional protein gel reproducibility and the effects of sample preparation, sample load, and image analysis

We investigate one approach to assess the quantitative variability in two-dimensional gel electrophoresis (2-DE) separations based on gel-to-gel variability, sample preparation variability, sample load differences, and the effect of automation on image analysis. We observe that 95% of spots present in three out of four replicate gels exhibit less than a 0.52 coefficient of variation (CV) in fluorescent stain intensity (% volume) for a single sample run on multiple gels. When four parallel sample preparations are performed, this value increases to 0.57. We do not observe any significant change in quantitative value for an increase or decrease in sample load of 30% when using appropriate image analysis variables. Increasing use of automation, while necessary in modern 2-DE experiments, does change the observed level of quantitative and qualitative variability among replicate gels. The number of spots that change qualitatively for a single sample run in parallel varies from a CV = 0.03 for fully manual analysis to CV = 0.20 for a fully automated analysis. We present a systematic method by which a single laboratory can measure gel-to-gel variability using only three gel runs.     

Novel nanomaterials used for sample preparation for protein analysis

Sample preparation is of vital importance for proteomic analysis because of the high complexity of biological samples. The rapid development of novel nanomaterials with various compositions, morphologies, and proper surface modifications provides a category of powerful tools for the sample preparation for protein analysis. In this paper, we have summarized recent progresses for the applications of novel nanomaterials in sample preparation for the analysis of proteomes, especially for phosphoproteomes, glycoproteomes, and peptidoms. Several kinds of novel nanomaterials were also discussed for their use in other kinds of proteomics analysis.