Probiotics Production: An Interesting Example for the Undergraduate Analytical Chemistry Laboratory

An analytical chemistry laboratory experiment for undergraduates that combines traditional analytical chemistry techniques with the interdisciplinary field of biotechnology is presented. It involves a process in which the combination of a yeast (Schizosacaromyces pombe) and a bacteria (Acetobacter xylimun), usually named Kombucha, in a very simple culture of commercial black tea and glucose produces metabolites that are sampled and quantified by students. Students determine the biomass and quantify the production of several organic acids, and the consumption of glucose. This is an interdisciplinary project where students apply many tools of the general analytical process and combine results obtained by all the participating students to learn the characteristics of a biotechnological process. Overall, the system discussed is easy to implement because the selected micro-organisms are not pathogenic, are safe and easy to manipulate, and are resistant to contamination.     

Analytical chemical laboratory exercises on basic and advanced level at the Technical University Budapest

An overview on the practical laboratory work done by the chemical engineering students is given at different levels of the curriculum of the Faculty of Chemical Engineering. Laboratory exercises and individual laboratory work is carried out at the following levels: Basic level. The different analytical chemical methods are acquisited by the students. Advanced level. A problem oriented project work is done with integrated use of the different analytical methods in the 8th semester. Thesis work. Specialized individual work on an elected research topic. Postgraduate courses. Organized for the understanding and practice of the latest methods and applications in the analytical chemistry. The programs of the different levels are detailed in the following. Received: 10 January 1996 / Accepted: 20 May 1996     

The degree of efficiency, the degree of reproducibility and the equivalence probability in statistical comparisons of analytical methods for the determination of tin in tin ores

Summary In most cases investigations concerning the reproducibility of different analytical methods for the determination of tin in tin ores consist only in comparisons of means, i.e. detection of systematic errors. The fact that the methods use different calibrating procedures, on the one hand, and that their accuracy varies, on the other hand, makes it necessary, to look for more sensitive criteria. For this purpose, the degree of efficiency regarding the determination of the true mean of a reference method, the degree of (mutual) reproducibility, and the equivalence probability are defined and their meaning is statistically interpreted. The degree of efficiency ɛ of any two methods is defined as the ratio of their mean square errors in determining the true mean of a reference method. This quantity can be described by the ratio of the upper bounds for the probabilities of an error by the two methods. The degree of reproducibility P* of different analytical methods we understand as minimal probability of comparable measuring results. The equivalence probability P_e is defined as a-posteriori probability of the hypothesis that the two distribution functions considered are identical. The criteria ɛ, P* and P_e seem to be more suitable for statistical comparisons as compared to known statistical standard procedures, such as the t-test criterion. The applicability of these quantities was checked by the example of 6 different methods for the determination of tin in tin ores. For this purpose, it was necessary to evaluate objectively the efficiency of sample division in order to get reproducible final samples for analysis using the hierarchical two-way classification of variance analysis. General knowledge concerning the analytical methods used could be completed.     

Ménage À Trois: Activation, Analysis and Uncertainty, 10 Projections into the Impending Millenium

For more than half a century we have been using activation of stable isotopes to determine chemical elements, and significant contributions have been made to a variety of scientific subjects. Nevertheless, activation analysis has not yet become integrated in the field of chemical analysis, and therefore the special features characteristic of activation analysis have not been fully realised in analytical chemistry. At the same time basic chemical knowledge has only to a limited extent been utilised in the development of analytical methods based on activation. This situation has only now become painfully clear, when a world-wide requirement is being made to express the uncertainty of analytical results in accordance with the BIPM philosophy. The identification and estimation of all uncertainty components needed to produce a reliable uncertainty budget requires the combined efforts of all parties. An attempt is here made to extrapolate current trends for the expression of uncertainty in activation and analysis into the future and to show, how the implementation of the BIPM Guidelines with respect to correction for all known or suspected biases, achievement of statistical control, and full traceability, can help bringing analytical chemistry into its rightful position as a scientific discipline in the field of metrology.     

New trends in methodological developments in clinical chemistry

Many new techniques have been introduced in clinical chemistry. Three important new methodologies are dry chemistry, gen technology and biosensors. Solid-phase chemistry systems. The two most common solid-phase systems are the Kodak-Ektachem and the Boehringer Mannheim Reflotron. The first one is working with serum and the second one mainly with whole blood. The determination of urea and the determination of the activity of AST (GOT) will be described. The greatest problems of these systems are the quality control of the analysis and the interferences by endogenous and exogenous substances. Analysis with the aid of gen technology. The major diagnostic applications of gen technology in human disease is the detection of genetic disorders and the tumor diagnosis. The beta-thalassemia will be the example for genetic disorders and the chronic myeloid leukemia (CML) for diagnosis of a tumor. Thalassemias are a group of inherited disorders caused by the defective or absent outpout of one of the globin chains of the Hb tetramere. The CML is an example of a specific translocation of a small region of chromosome 9 bearing the abl-oncogene to chromosome 22. Biosensors in biochemical analysis. Biosensors are analytical devices that respond selectively to analytes in an appropriate sample and convert their concentration into an electrical signal. As examples an in-vivo ferrocene-mediated glucose sensor and the determination of the isoenzyme LDH5 based on an antigene-antibody reaction are described.     

Quality assurance and statistical control

In scientific research laboratories it is rarely possible to use quality assurance schemes, developed for large-scale analysis. Instead methods have been developed to control the quality of modest numbers of analytical results by relying on statistical control: Analysis of precision serves to detect analytical errors by comparing thea priori precision of the analytical results with the actual variability observed among replicates or duplicates. The method relies on the chi-square distribution to detect excess variability and is quite sensitive even for 5–10 results. Interference control serves to detect analytical bias by comparing results obtained by two different analytical methods, each relying on a different detection principle and therefore exhibiting different influence from matrix elements; only 5–10 sets of results are required to establish whether a regression line passes through the origo. Calibration control is an essential link in the traceability of results. Only one or two samples of pure solid or aqueous standards with accurately known content need to be analyzed. Verification is carried out by analyzing certified reference materials from BCR, NIST, or others; their limited accuracy of 5–10% make them less suitable for calibration purposes.     

Total Lipid Extraction of Food Using d-Limonene as an Alternative to n-Hexane

A useful and green method for the extraction of fats and oils with a new procedure combining Soxhlet extraction and Clevenger distillation using d-limonene (bio-solvent) as a substitute for n-hexane (petroleum solvent) is reported. This method using green solvent is a laboratory exercise which easily teaches fundamental green analytical chemical lessons and successfully incorporates green “analytical chemistry” into the teaching and the research laboratory to both developed and developing nations.     

Further on creating normal density functions in Microsoft<Superscript>®</Superscript> Excel

Simulations play an increasing role in metrology and analytical chemistry, particularly the use of simulated normal distributions. Microsoft Excel is available to almost everybody and normal distributions can be simulated using either an innate function or other algorithms. We explore the success of five different algorithms to simulate normal distributions and compare the outcome with a simulation coded in R. The normality of 10⁶ data points simulated by the chosen algorithms was tested by different recognized statistical procedures and Q–Q plots. They all failed the statistical procedures, but evaluating the Q–Q plots revealed different types of deviations. It also showed that the deviations, although statistically significant, most likely do not have any practical relevance in laboratory work.     

Desorption of BTEX from activated charcoal using accelerated solvent extraction: evaluation of occupational exposures

A procedure for the determination of benzene, toluene, ethylbenzene and o-xylene, m-xylene and p-xylene (BTEX) in occupational environments is proposed. These compounds are extracted from activated charcoal using accelerated solvent extraction. Operational parameters are optimized and quantitative recovery is obtained using acetonitrile as the extraction solvent and 1-mL extraction cells, a preheat time of 2 min, a temperature of 160 °C, a pressure of 1,500 psi, a static period of 5 min, a flush volume of 110%, two cycles and a purge time of 90 s. Determination of BTEX compounds is carried out by gas chromatography using a flame ionization detector. The recoveries, obtained for a confidence level of 95%, are 91 ± 4, 100 ± 3, 104 ± 2, 93 ± 4, 99 ± 2 and 99 ± 2% for benzene, toluene, ethylbenzene, o-xylene, m-xylene and p-xylene, respectively. The detection limits are 0.5 μg for benzene, 0.7 μg for toluene and 1.0 μg for the other compounds. The proposed procedure has been applied to real samples collected in several workplaces, like a microbiology laboratory, an analytical chemistry laboratory, a printer’s, a car repair shop and a petrol station. From the results obtained, it can be concluded that the occupational exposures determined are always acceptable because they are lower than the tenth part of the recommended exposure limits (VLA-ED and VLA-EC).     

Conceptual polymorphism of entropy into the history: extensions of the second law of thermodynamics towards statistical physics and chemistry during nineteenth–twentieth centuries

After the birth of thermodynamics’ second principle—outlined in Carnot's Réflexions sur la puissance motrice du feu (1824)—several studies provided new arguments in the field. Mainly, they concerned the thermodynamics’ first principle—including energy conceptualisation—, the analytical aspects of the heat propagation, the statistical aspects of the mechanical theory of heat. In other words, the second half of nineteenth century was marked by an intense interdisciplinary research activity between physics and chemistry: new disciplines applied to the heat developed in the form of analytical, mechanical and statistical theories. Inside all these theories, entropy—the brand-new function that Clausius coined in his Mechanical theory of heat—started to play a central epistemic role. In the present paper, we analyse some steps of the historical process of conceptualisation of such function from 1850 to 1902. Particularly, we retrace the historical–foundational path that—starting from Clausius’ Second Law—lead Boltzmann and Gibbs to their distinguished formulations of statistical entropy. As usual, our research has been unrolled through the analyses of primary sources and by leaning on critical readings of the secondary literature. As for the methodological approach, text analysis of historical documents constituted our privileged modus operandi. This paper is the expression of a collaborative historical research program focused on the thermodynamic foundations of physics–chemistry relationship; early results have already been published by the same authors upon the concepts of reversibility––and––thermal equilibrium.

     

Multivariate calibration leverages and spectral F‐ratios via the filter factor representation

Diagnostics are fundamental to multivariate calibration (MC). Two common diagnostics are leverages and spectral F‐ratios and these have been formulated for many MC methods such as partial least square (PLS), principal component regression (PCR) and classical least squares (CLS). While these are some of the most common methods of calibration in analytical chemistry, ridge regression is also common place and yet spectral F‐ratios have not been developed for it. Noting that ridge regression is a form of Tikhonov regularization (TR) and using the unifying filter factor representation for MC, this paper develops the filter factor form of leverages and spectral F‐ratios. The approach is applied to a spectral data set to demonstrate computational speed‐up advantages and ease of implementation for the filter factor representation. Copyright © 2010 John Wiley & Sons, Ltd.     

Energy of activation and temperature for the hydrolysis of sucrose

We have reinvestigated temperature effects on the rates of hydrolysis of 0.0585M sucrose in 0.57M HCl solutions over the range of 10–40°C using polarimetry as a physical method to follow the reaction while simultaneously analyzing the solutions by HPLC for the disappearance of sucrose and by GLC for the appearance of glucose. When the polarimetric data are corrected for the mutarotation lag, the energy of activation values are the same by all three analytical methods and are temperature-independent.     

Flow Asymmetric Propargylation: Development of Continuous Processes for the Preparation of a Chiral β‐Amino Alcohol

The development of a flow chemistry process for asymmetric propargylation using allene gas as a reagent is reported. The connected continuous process of allene dissolution, lithiation, Li‐Zn transmetallation, and asymmetric propargylation provides homopropargyl β‐amino alcohol 1 with high regio‐ and diastereoselectivity in high yield. This flow process enables practical use of an unstable allenyllithium intermediate. The process uses the commercially available and recyclable (1S ,2R )‐N ‐pyrrolidinyl norephedrine as a ligand to promote the highly diastereoselective (32:1) propargylation. Judicious selection of mixers based on the chemistry requirement and real‐time monitoring of the process using process analytical technology (PAT) enabled stable and scalable flow chemistry runs.     

Amperometric Glucose Biosensing of Gold Nanoparticles and Carbon Nanotube Multilayer Membranes

A novel multilayer gold nanoparticles/multiwalled carbon nanotubes/glucose oxidase membrane was prepared by electrostatic assembly using positively charged poly(dimethyldiallylammonium chloride) to connect them layer by layer. The modification process and membrane structures were characterized by atomic force microscopy, scanning electron microscopy and electrochemical methods. This membrane showed excellent electrocatalytic character for glucose biosensing at a relatively low potential (?0.2 V). The K_m value of the immobilized glucose oxidase was 10.6 mM. This resulting sensor could detect glucose up to 9.0 mM with a detection limit of 128 μM and showed excellent analytical performance.     

A Specific Blend of Drakolide and Hydroxymethylpyrazines: An Unusual Pollinator Sexual Attractant Used by the Endangered Orchid Drakaea micrantha

Bioactive natural products underpin the intriguing pollination strategy used by sexually deceptive orchids. These compounds, which mimic the sex pheromones of the female insect, are emitted in particular blends to lure male insect pollinators of specific species. By combining methods from field biology, analytical chemistry, electrophysiology, crystallography, and organic synthesis, we report that an undescribed β‐hydroxylactone, in combination with two specific hydroxymethylpyrazines, act as pollinator attractants in the rare hammer orchid Drakaea micrantha. This discovery represents an unusual case of chemically unrelated compounds being used together as a sexual attractant. Furthermore, this is the first example of the identification of pollinator attractants in an endangered orchid, enabling the use of chemistry in orchid conservation. Our synthetic blend is now available to be used in pollinator surveys to locate suitable sites for plant conservation translocations.     

The Teaching/Learning Process in Analytical Chemistry

Before teaching a course, the instructor must identify what she or he intends for the students to learn. For most analytical chemistry instructors, this usually involves an assessment of what methods and techniques to include and at what depth to cover them. There are many other skills, though, that will be important to students for their future success. Most college classes in analytical chemistry are taught in a lecture format. Techniques that can be used to improve the learning that can occur during a lecture are described. An alternative to lecturing is the use of cooperative learning. Cooperative learning offers the potential to develop skills such as teamwork, communication, and problem-solving that are more difficult to impart in a lecture format. The laboratory component of analytical chemistry courses is often an underutilized learning resource. More often than not, the lab is used to demonstrate fundamental wet and instrumental analysis techniques and develop rudimentary laboratory skills. The analytical lab should also be used to develop meaningful problem-solving skills and to demonstrate and have students participate in the entire analytical process. Ways of enhancing the analytical laboratory to include more global skills that are important to career success are described.Received January 12, 2003; accepted March 7, 2003 Published online July 16, 2003     

Iodination of vanillin and subsequent Suzuki-Miyaura coupling: two-step synthetic sequence teaching green chemistry principles

ABSTRACT

A two-step synthetic sequence was developed for the undergraduate organic chemistry laboratory using vanillin as the starting material. The multi-step synthesis was designed to replace two traditional experiments teaching electrophilic aromatic substitution and carbon–carbon bond forming chemistries with greener transformations. Vanillin is iodinated using Oxone® and potassium iodide in refluxing water, and students are tasked with determining the position of aromatic substitution using ¹H NMR spectroscopy. The tan, shiny, pleasant-smelling iodovanillin is subsequently used in an aqueous Suzuki-Miyaura reaction with para-methylphenylboronic acid; strategically chosen to afford a second instructive ¹H NMR spectrum. Both conventional heating and microwave conditions can be employed for the palladium-catalyzed reaction. This synthetic sequence, successfully performed over multiple semesters by hundreds of students, models green chemistry principles through the use of a potentially renewable feedstock and safer reagents, the choice of water as a safer reaction solvent, and the employment of a catalytic reaction. Additionally, the sequence minimizes waste in teaching labs through use of an intermediate product.     

A practical analytical quality report on the effect of carotenemia on neonatal bilirubin levels

 The effect of haematocrit and β-carotene levels on the serum total bilirubin measurement in two analytical methods was studied as an example of the impact of practical analytical quality in medical decision making. The precision characteristics of the two methods were very similar. Based upon the significant difference in the correlation coefficient in a method comparison study before and after 20% trimming of the data, an interference effect study was performed. Haemoglobin (expressed as haematocrit) and β-carotene were the substances studied to explain the observed differences. The bilirubin test results from the Wako bilirubinometer were easily affected (n=19;X(S): 13.83±2.43;t=–6.17;P=0.000) and more elevated than in the Vitros dry chemistry systems (n=18;X(S): 12.72±2.21;t=–2.48;P=0.017), due to the presence of β-carotene (>200 μg/dl).     

Origin自定义非线性拟合在分析化学实验中的应用

介绍了Origin软件中用户自定义非线性拟合功能的使用方法,并结合实例讨论如何应用非线性拟合对分析化学实验数据进行处理。结果表明,该方法能准确计算实验结果、对实验数据进行评价,同时还可方便得到绘制的图表,应在分析化学实验教学中推广应用。