A computer language for reducing activation analysis data

A program, written in FORTRAN, is described that defines a language for reducing activation analysis data. Communications are effected through commands, and these can be given in almost any order. Consistency checks are done and diagnostic messages are printed automatically to guard against the incorrect use of the commands. Default options on the commands allow instructions to be expressed concisely while providing a capability to specify details for the data reduction process. The program has been implemented on a UNIVAC 1108 computer.     

A centralized,hierarchically structured computer system for chemical research and analytical instrumentation

An hierarchically structured, centralized compute system, replacing an obsolete central DECsystem-10, can be used for all the computational tasks in chemical research, as well as for real-time data acquisition and evaluation for numerous analytical instruments, required in a large Institute. In this hierarchical system, the real-time tasks are done by local minicomputer satellites that are tailored to special requirements in the laboratories. All higher level data processing and data storage demands are covered by the central system, consisting of two VAX11/780 computers, to which all satellites as well as all user terminals are connected. The design criteria are described as well as some of the software packages developed for this system.     

A computer system for structural identification of organic compounds from 13C NMR data

A computerised library search system for ¹³C NMR data is described. Given the spectral data of an unknown compound, the system will retrieve from the library those reference compounds exhibiting similar spectra. For comparison the spectral data are converted into a binary code, designed to reflect the underlying structure rather than exact values for chemical shifts. Thus, the ability of the system to retrieve compounds similar to the unknown (as opposed to identical) is greatly enhanced. A sophisticated search strategy adapting itself automatically to the problem at hand makes the system highly efficient.     

A computer program system for kinetic analysis of non-isothermal thermogravimetric data: I. Data acquisition and preparation for kinetic analysis

FORTRAN software is described which enables the generation of rate of weight change data (DTG) from percentage weight change measurements (TG), obtained under non-isothermal conditions. The program also transposes this information into the dimensionless extent and rate of reaction at unit temperature intervals by means of a cubic spline interpolation. A simple search routine identifies all DTG spikes in the thermogravimetric record, and the temperature and extent of reaction at which the rate attains its maximum value. This total information serves as input data for the kinetic analysis software to be discussed in part II of this communication. An example of the application of this program to the pyrolysis of bituminous coal is presented.     

A small computer data system for low resolution magnetic deflection mass spectrometers

A small on-line computer system for complete processing of low resolution magnetic deflection mass spectrometric data has been demonstrated. An interpolated mass scale accuracy of 200ppm was achieved for both repetitive (five or ten second cycle times) and single scan modes. Identification of m/e values above 1000 is possible with an accuracy of 500 ppm to m/e 3600. Mass scale assignments are time based and externally calibrated (pfa).     

A computer program system for kinetic analysis of non-isothermal thermogravimetric data: II. Generalized kinetic analysis and application to coal pyrolysis

A FORTRAN program is presented which enables the kinetic analysis of extent and rate of reaction data resulting from transposed experimental TG/DTG data obtained under non-isothermal conditions. This software allows one to perform Arrhenius, Friedman and Kissinger analyses for up to nine different solid-state rate-controlling reactions, including nth order, Avrami-Erofeev, phase boundary movement and diffusional models. Data from an investigation of the pyrolysis of a bituminous coal serve as an example of the application of the program.     

A computer system for the spectrometric analysis of high alloyed steel

Summary Experiences with a computer controlled analyser system for production control in a steel plant are reported. The analyser system consists of a direct reading vacuum spectrometer, a digital computer and a data transmission system. The computer system is responsible for the control of the spectrometer as well as for the transformation of measured values into element concentration values and their transmission into the plant internal teleprinter network. A great disadvantage of spectrometers is the fact that matrix effects occur. To solve the problems arising from that — especially in the case of analyses of an extended alloying program — either numerous special calibration curves for all the different types of alloyed steels can be established or one can use only one calibration curve and eliminate the matrix effects by calculation of the line coincidences and the third element influences. The combination of a spectrometer and a digital computer permits rapid determination of the chemical composition of samples by following the second procedure and makes the automatic transmission and documentation of data possible. The composition and working method of such an equipment is described, some selected examples for the used method of calibration are given. The principle of the digital computer program for the calculation of the chemical composition from measured intensity values is demonstrated, and the means of automatic transmission of results are shown. The main advantages of the system and also its limits are discussed.     

Flow injection analysis system for on-line cutinase activity assay

A FIA system based on a micellar system for a substrate (p-nitrophenylbutyrate) with low stability in aqueous phase was built to monitor cutinase activity in bioprocesses. All samples were previously diluted with 50 mM phosphate buffer pH 7.0 containing 11.6 mM sodium cholate. The cutinase activity in this diluted solution enhances about 40% in relation to phosphate buffer. Furthermore, the enzyme adsorption and consequent blocking/fouling of injector and tubes of the FIA system was eliminated due to excellent properties of sodium cholate as surface active agent.The cutinase activity is based in following the hydrolysis of p-nitrophenylbutyrate to p-nitrophenol in the reaction stream through the formation of an absorbance peak at 400 nm proportional to enzyme activity. The compositions of reaction stream as well as its stability were studied in order to minimize non-enzymatic hydrolysis of p-nitrophenylbutyrate and maximize cutinase activity assay reproducibility. An excellent correlation was obtained between the FIA system and off-line method for determination of cutinase activity in the culture media, and during separation of Saccharomyces cerevisiae cells and cutinase concentration by micro and ultrafiltration, respectively.     

Cascade system for rapid on-line dilutions in flow-injection analysis

A system for on-line dilutions in flow-injection analysis (FIA) is described. The system requires two flow-through pumps (peristaltic) and a conventional rotary injection valve. No precision timing or computer-controlled valves are required. The "cascade" dilution technique is demonstrated by the determination of 0-1.7M chloride. Viscosity effects are studied for samples with viscosities of 1-150 relative to water. Sample-zone volume reduction by splitting streams is combined with dilution by merging streams to achieve effective dilution factors of nearly 500. The reciprocal mole fraction is proposed as a variable for the characterization of open flow-injection systems and compared with the dispersion coefficient. An equation is included to predict this factor as a function only of the flow-rates used in the system. The cascade dilution system yields reproducible dilution factors with relative standard deviations of less than 3%, with sampling rates up to 100/hr.     

A microcomputer-based data acquisition and processing system for electrochemical analysis

The system described for electrochemical analysis includes ensemble averaging, boxcar integration and background subtraction. A digital storage oscilloscope interfaced to a microcomputer provides these data-processing techniques for the differential pulse polarographic determination of molybdenum. The system is easily interfaced to the polarograph. An approximately four-fold improvement in the detection limit for molybdenum — to 2.7 × 10^-4 ppm — was achieved by using a combination of ensemble averaging and background subtraction.     

A new analytical system for multicomponent gas-chromatographic analysis of metabolites in biological material

Summary A new method for the gas-chromatographic multicomponent analysis of metabolites in biological material is described. It is an analytical procedure involving several extractions carried out under different conditions. In this procedure the metabolites are divided according to their functional groups and specific chemical behaviours into eight main fractions: lipids, hydrocarbons, organic acids, neutral substances, phenols, amines, amino acids and carbohydrates. Each of these fractions is derivatized; the components are separated and estimated by gas chromatography. This analytical system was applied to the determination of a number of metabolites in serum, urine, amniotic fluid, sperma, tissues and other biological materials.

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Neues Analysensystem zur Multikomponenten-GC-Analyse von Metaboliten in biologischem Material

Zusammenfassung Eine Methode für die Multikomponenten-GC-Analyse von Metaboliten in Biomaterialien wird beschrieben. Das Verfahren umfaßt mehrere Extraktionen, die unter verschiedenen Bedingungen durchgeführt werden. Die Komponenten werden in Abhängigkeit von ihren funktionellen Gruppen und spezifischem chemischen Verhalten in acht Hauptfraktionen geteilt: Lipide, Kohlenwasserstoffe, organische Säuren, neutrale Substanzen, Phenole, Amine, Aminosäuren und Kohlenhydrate. Die Komponenten jeder Gruppe werden nach spezieller Derivatisierung gaschromatographisch getrennt und bestimmt. Dieses neue System ist bei verschiedenen biologischen Materialien (klinische Proben, Pflanzen- und Tiergewebe) angewandt worden.

     

A review of on-line analysis

Practical analytical devices only become generally available when there has been a meaningful relationship between users, researchers, equipment manufacturers and the suppliers of capital. In order to obtain good value from capital investment, the analytical engineer must assess initial requests for work constructively. The cost return from process analysis depends not only on good maintenance planning but also on the confidence of the users. Apart from signal correction and processing, microelectronics are now commonly used to auto-diagnose analyser faults. This both aids maintenance and reassures the owner. Sampling systems, a key factor in analytical practice, often lead to a difference in the results from process and laboratory analysis. Laboratory automation is narrowing the gap between on and off-line analytical systems. Some major techniques are briefly reviewed with comments on possible trends and applications.On-line chemical analysis owes its charm and its very existence to the melding of ideas from a multitude of sciences and technologies. Serious practitioners make it their business to foster new contacts to glean, record, and barter ideas, even from fields which, at first sight, appear unrelated. Users, researchers and equipment manufacturers should continually review their own positions to create meaningful relationships with each other and build strong links in chemical measurement and on-line analysis.     

A data acquisition system for mass-analyzed ion kinetic energy spectra using a personal computer

An inexpensive data acquisition system has been developed for mass-analyzed kinetic energy experiments which involve scanning the electrostatic analyzer of a reversed geometry mass spectrometer. The various hardware and software design features are described. Results for data obtained with a commercially available VG ZAB-2F mass spectrometer are presented and discussed.     

The design of an on-line semi-preparative LC-SPE-NMR system for trace analysis

This paper reports the design of an on-line semi-preparative LC-SPE-NMR system and its use in the structural analysis of mixture components at the 0.02-1% level. The combination provides at least a five fold mass sensitivity increase over that obtained from typical analytical LC-SPE systems and a >30-fold total NMR sensitivity enhancement over analysis by LC-NMR. This is accomplished by using a novel on-line device to store, dilute (1-100-fold) and deliver (at an optimized flow-rate) the isolated component of interest to an SPE trap unit. The SPE unit consists of two cartridges connected in parallel to increase the overall SPE capacity and also to decrease the flow-rate through each trap for enhanced trapping efficiency. As the coupling of semi-preparative LC with NMR (through SPE) is well matched in terms of optimal mass loading for both techniques, only one LC-SPE cycle is required to enrich a 50 microg ml(-1) component (1% in a 5 mg ml(-1) mixture) for the acquisition of heteronuclear (1)H-(13)C NMR data using a conventional NMR flow probe. Furthermore, analytes at the 0.02% level (approximately 1 microg ml(-1)) can be studied using 2D (1)H NMR techniques if peak cuts from replicate sample injections (> or =3) are accumulated into the storage/dilution unit and the resulting solution processed by just one SPE trap and elute cycle.     

Sequential injection system for on-line analysis of total nitrogen with UV-mineralization

An automatic method for the determination of total nitrogen in wastewater by sequential injection analysis and mineralization with UV radiation has been developed. The method is based on the mineralization of the samples with sodium persulphate in basic medium under UV radiation. Small volumes of sample and reagents are firstly aspirated into a single channel and then propelled by flow reversal to the UV reactor and then to the detector. The organic and inorganic nitrogen compounds are oxidized to nitrate that is then measured at 226 nm. The sequential injection procedure has been optimized and the factors affecting the efficiency of the oxidation have been studied with a number of test substances with different chemical structures and properties. Solutions in the concentration range 1-56 g l⁻¹ of nitrogen can be analyzed with the described procedure. The sample rate is of 30-40 samples h⁻¹. The LOD is 0.6 mg l⁻¹ N and the reproducibility is 1.8% (28 mg l⁻¹ N). Organic carbon in the form of glucose was added to a number of test solutions to study the potential interference of organic matter.The method was compared with the Kjeldahl digestion method by analyzing 15 wastewater samples with both methods. The nitrate and nitrite content of the non-oxidized samples were subtracted from the corresponding nitrogen content determined after photo-oxidation and the value compared with the Kjeldahl nitrogen content.     

A computer program for ranking analytical methods according to their fitness for purpose

A program for conducting automatic searches for analytical methods, selecting the most suitable ones according to quality requirements, and ranking them based on quality indices calculated from various pre-selected quality parameters is proposed. The program uses an externally updated database (Analytical Abstracts CD-ROMs or other) and customised quality schemes based on accuracy, precision, sensitivity, applicability to real samples, determination range (ratio), throughput and impact factor (from the Citation Index). It can, therefore, be used for a variety of purposes in analytical chemistry.     

A continuous liquid-liquid extraction system coupled on-line with capillary gas chromatography for environmental and ecotoxicological analysis

The applicability of a liquid-liquid extraction system which is coupled on-line with a capillary gas chromatograph was studied for environmental and ecotoxicological analyses. The optimized and automated system was used for the determination of apolar and rather non-volatile organic compounds in aqueous samples. Relevant aspects of sample introduction, phase separation and selection of extraction solvent are discussed. Three routine-tipe applications are described, viz. an improved method for the determination of hexachlorocyclohexanes in ground water and the determination of the so-called NCC-ether and ACC-ether in ecotoxicological studies. Depending on the application studied, the concentration levels varied from 0.1 to 6000 μg/I, using ECD and/or FID detection. Typical coefficients of variation obtained with the total extraction–GC procedure were 2–25%. The system was found to be rugged, it saves time compared with set-ups involving off-line liquid-liquid extraction and considerably reduces the manual work load.