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  • Analytical Chemistry and Spectroscopy  (2,155)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 21-36 
    ISSN: 0886-9383
    Keywords: GRAM ; Tucker ; Unfold ; NBRA ; Second-order ; Three-way ; PARAFAC ; Trilinear ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: If an analytical instrument or instrumental method gives a response matrix when analyzing a pure analyte, the instrument or instrumental method is called a second-order method. Second-order methods that generate a response matrix for a pure analyte of rank one are called rank-one second-order methods. If the response matrix of a pure analyte is not rank one, essentially two cases exist: medium rank (between two and five) and high rank (greater than five). Subsequently, medium- and high-rank second-order calibration tries to use medium- and high-rank second-order methods to analyze for analytes of interest in a mixture. A particular advantage of second-order methods is the ability to analyze for analytes of interest in a mixture which contains unknown interferences. Keeping this advantage is the challenge on moving away from rank-one second-order calibration methods. In this paper a medium-rank second-order calibration method is proposed based on least-squares restricted Tucker models. With this method the second-order advantage is retained.
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  • 2
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 101-101 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 3
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 103-110 
    ISSN: 0886-9383
    Keywords: Taguchi ; Robust design ; Design of experiments ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper is intended to convey the essence of Taguchi's design approach to chemists and others with an interest in chemometrics. Although most Taguchi-style applications worldwide have been in electronics and in elaborately transformed manufactures, examples are increasingly found in chemical processes and in the food industry.Foremost among Taguchi's contributions is the concept of designing processes and products to be robust to the uncontrollable environmental influences which they experience during their operation or lifetime. This concept is explained with a worked example.
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  • 4
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. 127-145 
    ISSN: 0886-9383
    Keywords: Compression ; Multivariate analysis ; B-splines ; FT-IR spectra ; Second-order ; Two-dimensional ; Hyphenated methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In order to improve the storage and CPU time in the numerical analysis of large two-dimensional (hyphenated, second-order) infrared spectra, a data-preprocessing technique (compression) is presented which is based on B-splines. B-splines have been chosen as the compression method since they are wellsuited to model smooth curves. There are two primary goals of compression: a reduction of file size and a reduction of computation when analyzing the compressed representation. The compressed representation of the spectra is used as a substitute for the original representation. For the particular example used here, approximately 0.16 bit per data element was required for the compressed representation in contrast with 16 bits per data element in the uncompressed representation. The compressed representation was further analysed using principal component analysis and compared with a similar analysis on the original data set. The results shows that the principal compotent model of the compressed representation is directly comparable with the principal component model of the original data.
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  • 5
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 6
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 7
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    Journal of Chemometrics 8 (1994), S. 181-203 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalues ; Bias ; Variance ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this second paper expressions are derived for predicting the bias and variance in the eigenvalues of GRAM. These expressions are built on the analogies between a reformulation of the eigenvalue problem and the prediction equations of univariate and multivariate calibration. The error analysis will also be performed for Lorber's formulation of RAFA. It will be demonstrated that, depending on the size of the eigenvalue, large differences in performance must be expected. A bias correction technique is proposed that effectively eliminates the bias if the error in the bias estimate is not too large. The derived expressions are evaluated by Monte Carlo simulations. It is shown that the predictions are satisfactory up to the limit of detection. The results are not sensitive to an incorrect choice of the dimension of the factor space.
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  • 8
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    Journal of Chemometrics 8 (1994), S. 243-243 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 9
    ISSN: 0886-9383
    Keywords: Fitting ; Non-linear ; Least squares ; Refinement ; Constraints ; MSE ; Confidence ; C ls ; XPS ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A non-linear least squares iterative refinement has been implemented which shows high performance on a multiple-peak spectrum including baseline or background. Constraints as well as links within a range are introduced to drive the mathematical optimization: each peak parameter (i.e. height, position, Gaussian/Lorentzian mixing ratio and HWHM on both left and right sides) has assigned to it an allowed range of variation and can be strained to be correlated with other parameters belonging either to the same peak (symmetrical peaks) or to other peaks (doublets, triplets, etc.). Peak shapes typical of XP spectra are used and applications in the field of XPS are discussed. Through emulated curves with Poisson distributed noise, the accuracy and precision of back-calculated (refined) parameters have been estimated. Moreover, a confidence level calculated from X2 and degrees of freedom has been suggested to check the overall fitting of experimental curves where the signal-to-noise ratio is a priori unknown. An application to real C ls XP spectra is described as an example and a list of suggestions is given to match operator requirements. Finally, features of NLLSRC are discussed with respect to other approaches.
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  • 10
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    Journal of Chemometrics 8 (1994), S. 263-272 
    ISSN: 0886-9383
    Keywords: Molecular descriptors ; Principal component analysis ; Chemometrics ; Pattern recognition ; Total surface area ; PCDD PCDF ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: New theoretical molecular indices are defined. They contain information about the whole molecular structure in terms of size, shape, symmetry and atom distribution. These indices are calcualted from the (x, y, z) co-ordinates of a molecule within different weighting schemes in a straightforward manner and represent a very general approach to describe molecules, molecular fragments, macromolecules and molecular conformations in a unitary conceptual framework. Their interpretability is quite evident and is defined by the same mathematical properties as the algorithm used for their calculation. Examples on the total surface area, toxicity of PCDD and PCDF and reaction rate of catalysed reactions show a high modelling power of these indices.
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  • 11
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    Journal of Chemometrics 8 (1994), S. 301-302 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 12
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    Journal of Chemometrics 8 (1994), S. 333-347 
    ISSN: 0886-9383
    Keywords: PLS ; ATR ; Paper ; Resolution ; Infrared ; FTIR ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Attenuated total reflectance Fourier transform infrared spectrometry (ATR-FTIR) has been used to determine the amount of styrene-butadiene latex on the surface of coated papers and to predict the composition of the polymer. Spectrum recording was performed on the sample in its usual form without any modification.For quantitative analysis, partial least squares (PLS) regression, principal component regression (PCR) and multi-linear regression (MLR) were used to calculate models for prediction. The best result is obtained with PLS.We analysed two series of paper samples. The first analysis concerns the measurement of the quantity of latex of a constant quality on the coating surface. For 15 samples the concentration varied between 5 and 25 parts (grams per 100g of mineral pigments). We compared the predictive results at various resolutions. We obtained a relative error of 0.15 parts in latex at 4 cm-1 resolution. The second analysis concerns the measurement of the styrene/butadiene ratio in various types of latex. We obtained a relative error of 0.156 parts for styrene determination and 0.161 parts for butadiene determination.
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  • 13
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    Journal of Chemometrics 8 (1994), S. 375-376 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 14
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    Journal of Chemometrics 8 (1994), S. 391-407 
    ISSN: 0886-9383
    Keywords: Neural networks ; Non-linear multivariate regression ; Pattern classification ; Kalman filter ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Finding methods for the optimization of weights in feedforward neural networks has become an ongoing developmental process in connectionist research. The current focus on finding new methods for the optimization of weights is mostly the result of the slow and unreliable convergence properties of the gradient descent optimization used in the original back-propagation algorithm. More accurate and computationally expensive second-order gradient methods have displaced earlier first-order gradient optimization of the network connection weights. The global, extended Kalman filter is among the most accurate and computationally expensive of these second-order weight optimization methods. The iterative, second-order nature of the filter results in a large number of calculations for each sweep of the training set. This can increase the training time dramatically when training is conducted with data sets that contain large numbers of training patterns. In this paper an adaptive variant of the global, extended Kalman filter that exhibits substantially improved convergence properties is presented and discussed. The adaptive mechanism permits more rapid convergence of network training by identifying data that contain redundant information and avoiding calculations based on this redundant information.
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  • 15
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    Journal of Chemometrics 8 (1994), S. 439-443 
    ISSN: 0886-9383
    Keywords: Pattern recognition ; Principal component analysis ; Inverse mapping ; Optimization ; Material design ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An inverse mapping method called PCB (principal component backing), in which the point representing an unknown sample from a low-dimensional principal component subspace is back-projected to the high-dimensional original feature space, is proposed. Two sorts of boundary conditions, non-linear inverse mapping and linear inverse mapping, are used to obtain an accurate solution in the PCB method. The method is applied to the material design of high-Tc superconductors, predicting the composition and process conditions for the synthesis of F-doped Bi-based materials. Samples in the ‘optimal’ region with the highest Tc of the Bi-based ceramics have been predicted.
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  • 16
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    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 17
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    Journal of Chemometrics 8 (1994), S. 37-44 
    ISSN: 0886-9383
    Keywords: Bootstrap ; Confidence interval ; Non-linear regression ; Monte Carlo methods ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Non-linear regression models describing the toxicity of a mixture of rotenone and pyrethrins as an insecticide, the catalytic dehydration of n-hexyl alcohol and the Michaelis-Menten model for characterizing reaction rates in enzyme systems will be used to illustrate the accuracy of bootstrap methods in non-linear regression. Classical and bootstrap confidence intervals for the parameter estimates will be presented.
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  • 18
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 19
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    Journal of Chemometrics 8 (1994), S. 102-102 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 20
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    Journal of Chemometrics 8 (1994), S. 111-125 
    ISSN: 0886-9383
    Keywords: PLS regression algorithm ; Kernel ; Many-variable data sets ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A fast PLS regression algorithm dealing with large data matrices with many variables (K) and fewer objects (N) is presented For such data matrices the classical algorithm is computer-intensive and memory-demanding. Recently, Lindgren et al. (J. Chemometrics, 7, 45-49 (1993)) developed a quick and efficient kernel algorithm for the case with many objects and few variables. The present paper is focused on the opposite case, i.e. many variables and fewer objects. A kernel algorithm is presented based on eigenvectors to the ‘kernel’ matrix XX TYYT, which is a square, non-symmetric matrix of size N × N, where N is the number of objects. Using the kernel matrix and the association matrices XXT (N × N) and YYT (N × N), it is possible to calculate all score and loading vectors and hence conduct a complete PLS regression including diagnostics such as R2. This is done without returning to the original data matrices X and Y. The algorithm is presented in equation form, with proofs of some new properties and as MATLAB code.
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  • 21
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    Journal of Chemometrics 8 (1994), S. 169-174 
    ISSN: 0886-9383
    Keywords: Kernel algorithm ; PLS ; SVD ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lindgren et al. (J. Chemometrics, 7, 45-49 (1993)) published a so-called kernel algorithm for PLS regression of Y against X when the number of objects is very large. The algorithm is based solely on deflation of the cross-product matrices XTX, YTY and XTY. The algorithm is now described in a shorter and more transparent way and compared with a similar algorithm for the singular value decomposition of XTY.
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  • 22
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    Journal of Chemometrics 8 (1994) 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 23
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    Journal of Chemometrics 8 (1994), S. 241-241 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 24
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    Journal of Chemometrics 8 (1994), S. 273-285 
    ISSN: 0886-9383
    Keywords: GRAM ; Least-squares problem ; Eigenvalue problem ; NIPALS ; Performance index ; Condition number ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In this paper we discuss the practical implementation of the generalized rank annihilation method (GRAM). The practical implementation comes down to developing a computer program where two critical steps can be distinguished: the construction of the factor space and the oblique rotation of the factors. The construction of the factor space is a least-squares (LS) problem solved by singular value decomposition (SVD), whereas the rotation of the factors is brought about by solving an eigenvalue problem. In the past several formulations for GRAM have been published. The differences essentially come down to solving either a standard eigenvalue problem or a generalized eigenvalue problem. The first objective of this paper is to discuss the numerical stability of the algorithms resulting from these formulations. It is found that the generalized eigenvalue problem is only to be preferred if the construction of the factor space is not performed with maximum precision. This is demonstrated for the case where the dominant factors are calculated by the non-linear iterative partial least-squares (NIPALS) algorithm. Several performance measures are proposed to investigate the numerical accuracy of the computed solution. The previously derived bias and variance are proposed to estimate the number of physically significant digits in the computed solution. The second objective of this paper is to discuss the relevance of theoretical considerations for application of GRAM in the presence of model errors.
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  • 25
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    Journal of Chemometrics 8 (1994), S. 299-301 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 26
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 27
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    Journal of Chemometrics 8 (1994), S. 349-363 
    ISSN: 0886-9383
    Keywords: Variable selection ; PLS ; Calibration ; Modelling ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A modified PLS algorithm is introduced with the goal of achieving improved prediction ability. The method, denoted IVS-PLS, is based on dimension-wise selective reweighting of single elements in the PLS weight vector w. Cross-validation, a criterion for the estimation of predictive quality, is used for guiding the selection procedure in the modelling stage. A threshold that controls the size of the selected values in w is put inside a cross-validation loop. This loop is repeated for each dimension and the results are interpreted graphically. The manipulation of w leads to rotation of the classical PLS solution. The results of IVS-PLS are different from simply selecting X-variables prior to modelling. The theory is explained and the algorithm is demonstrated for a simulated data set with 200 variables and 40 objects, representing a typical spectral calibration situation with four analytes. Improvements of up to 70% in external PRESS over the classical PLS algorithm are shown to be possible.
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  • 28
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    Journal of Chemometrics 8 (1994), S. i 
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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  • 29
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    Journal of Chemometrics 8 (1994), S. 409-421 
    ISSN: 0886-9383
    Keywords: Deconvolution ; FT-IR spectroscopy ; Protein conformations ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In a variety of spectroscopic techniques the fundamental problem exists of determination of the individual spectral components, intrinsically overlapped in the measured spectrum. This is a typical deconvolution problem and several methods and techniques have been proposed for its solution in the technical literature, but suggestions of new approaches are still of interest. A new deconvolution procedure is presented here based on the use of the conjugate gradient minimization algorithm with the addition of sutiable constraints directly obtained by the application to the measured spectrum of the second-derivative operator or more sophisticated resolution enhancement procedures. Since in the examined case deconvolution essentially requires the minimization of a non-convex function, the use of such constraints is extremely important to supply suitable input parameters to the conjugate gradient algorithm to avoid obtaining minimum points which have no physical meaning. In our case each spectral compoent used for deconvolution has been assumed to have a Gaussian analytical definition fully identified by three parameters (amplitude, central frequency, spectral bandwidth), so that the input values required to start the deconvolution process are the number M of Gaussian components and 3M suitable initial approximations of the parameters above. It is shown that all this information can be obtained from the measured data. The deconvolution procedure was implemented by a FORTRAN Microsoft Version 5.1 program and experimental results relative to spectroscopic data obtained by FT-IR analysis of human serum albumin are reported. The results are discussed and compared with data obtained by the use of other techniques.
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  • 30
    ISSN: 0886-9383
    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Topics: Chemistry and Pharmacology
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  • 31
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 32
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    Journal of Chemometrics 8 (1994), S. 1-20 
    ISSN: 0886-9383
    Keywords: Discriminant analysis ; Least squares ; Prediction ; Regression ; Relationship ; Structure ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Twenty-two contrasting statistical methods are reviewed for their applicability to QSAR studies and similar prediction-oriented fields. Each method is concisely specified prior to explanatory or critical comment.
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  • 33
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    Journal of Chemometrics 8 (1994), S. 65-79 
    ISSN: 0886-9383
    Keywords: Genetic algorithms ; Full validation ; Feature selection ; Outlier detection ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Genetic algorithms have been proved to be a very efficient method in the feature selection problem. However, as for every other method, if the validation of the results is performed in an incomplete way, erroneous conclusions can be drawn. In this paper a development of a previous genetic algorithm is presented so that a full validation of the results can be obtained. Furthermore, this algorithm has been shown to perform very well also as an outlier detector, allowing easy identification of the presence of outliers even in cases where the ‘classical’ techniques fail.
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  • 34
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    Journal of Chemometrics 8 (1994), S. 81-93 
    ISSN: 0886-9383
    Keywords: Sensory evaluation ; Cumulative ranks ; Assessor variation ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A graphical method of assessing differences between sets of rankings based on cumulative ranks is developed. The method can be used to identify rankings that differ over all or just part of the range of objects ranked. The method is applied to an example of sensory evaluation of green peas in which ten assessors scored six attributes on each of 60 samples.
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 305-331 
    ISSN: 0886-9383
    Keywords: Pyrolysis ; Mass spectroscopy ; Multivariate analysis ; Biological material identification ; Convexity ; Cones ; Subspaces ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work addresses the classification of high-dimensional time-dependent pyrolysis mass spectra of biological samples. The aim was the detection and classification of biological agents, and the developed approach resembles mixture analysis. The data were projected on to a low-dimensional subspace using singular value decomposition. Then a convex cone was formed on this subspace, showing as its corners physically meaningful components of the sample. This technique enabled separation of a biological material signal largely independent of the absolute amount of sample. The detection of the presence of any biological material could be accomplished based on the convex cone alone, without other reference to the mass spectra. Automated clustering of samples was successfully carried out using a minimal spanning tree.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 377-389 
    ISSN: 0886-9383
    Keywords: Kernel PLS regression ; Cross-validation ; Model dimensionality ; Multivariate image regression ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Multivariate images are very large data structures and any type of regression for their analysis is very computer-intensive. Kernel-based partial least squares (PLS) regression, presented in an earlier paper, makes the calculation phase more rapid and less demanding in computer memory. The present paper is a direct continuation of the first paper. In this study the kernel PLS algorithm is extended to include cross-validation for determination of the optimal model dimensionality. To show the applicability of the kernel algorithm, two examples from multivariate image analysis are used. The first example is an image from an airborne scanner of size 9 × 512 × 512. It consists of nine images which are regressed against a constructed dependent image to test the accuracy of the kernel algorithm when used on large data structures. The second example is a satellite image of size 7 × 512 × 512. Several different regression models are presented together with a comparison of their predictive capabilities. The regression models are also used as examples for showing the use of cross-validation.
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    Journal of Chemometrics 8 (1994), S. 99-100 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 41
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    Journal of Chemometrics 8 (1994), S. 147-154 
    ISSN: 0886-9383
    Keywords: RAFA ; GRAM ; Eigenvalue problem ; Complex solution ; Degenerate solution ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rank annihilation factor analysis (RAFA) is a method for multicomponent calibration using two data matrices simultaneously, one for the unknown and one for the calibration sample. In its most general form, the generalized rank annihilation method (GRAM), an eigenvalue problem has to be solved. In this first paper different formulations of GRAM are compared and a slightly different eigenvalue problem will be derived. The eigenvectors of this specific eigenvalue problem constitute the transformation matrix that rotates the abstract factors from principal component analysis (PCA) into their physical counterparts. This reformulation of GRAM facilitates a comparison with other PCA-based methods for curve resolution and calibration. Furthermore, we will discuss two characteristics common to all formulations of GRAM, i.e. the distinct possibility of a complex and degenerate solution. It will be shown that a complex solution-contrary to degeneracy-should not arise for components present in both samples for model data.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 179-180 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 287-292 
    ISSN: 0886-9383
    Keywords: Rank annihilation ; Principal components ; Procrustes rotation ; Multivariate analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is shown that the DATa ANalysis (DATAN) algorithm can be expressed in terms of rank annihilation factor analysis (RAFA). Subsequent advances in RAFA are applied to DATAN to eliminate the problems and restrictions associated with DATAN. The extension of DATAN in terms of the trilinear decomposition algorithm is discussed.
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 365-370 
    ISSN: 0886-9383
    Keywords: Censored data ; ECM and EM algorithms ; Incomplete data ; Maximum likehhood ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The purpose of this short communication is to illustrate the use of conditional maximization (CM) in chemometric applications. The CM algorithm is useful in reducing the computational complexity when a high-dimensional and complicated maximization problem arises from fitting chemometric models. It can also be efficiently combined with the expectation-maximization (EM) algorithm for handling incomplete data, a problem that sometimes arises when only a part of the intended data can be collected. Three models from fluorescence spectroscopy are used for illustration.
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 423-437 
    ISSN: 0886-9383
    Keywords: Resolvability ; Evolutionary factor analysis ; Variable selection ; Window factor analysis ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method for selecting variables in the non-sequential direction of a two-way data matrix (e.g. wavelength in diode array HPLC) is described. Composition 1 and 2 resolvability indices are calculated according to the size of eigenvalues of uncentred data matrices as a window is moved along the sequential direction. A double-window technique is then performed where resolvability indices are calculated as a window is moved along the non-sequential direction. Some regions have higher resolvability indices and hence are more useful for resolution. Variables are ranked according to resolvability. Two simulations are analysed and it is shown that it is possible to obtain good resolution on a small subset of the original variables.
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    Journal of Chemometrics 8 (1994), S. i 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 45-63 
    ISSN: 0886-9383
    Keywords: GRAM ; GSVD ; Propagation of errorS ; Correlated noise ; Uncorrelated noise ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of correlated and uncorrelated random errors on the precision of predicted quantitative and qualitative information obtained by analysis with the generalized rank annihilation method (GRAM) are shown. These are discussed in terms of propagation of errors through the algorithm. The effects of colinearity, noise level and noise distribution are compared and discussed.
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    Journal of Chemometrics 8 (1994), S. 97-98 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 155-168 
    ISSN: 0886-9383
    Keywords: Trilinear models ; Tensorial resolution ; PARAFAC ; Swamps ; Two-factor degeneracy ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The alternating least squares PARAFAC algorithm is a useful tool for resolving trilinear three-way data arrays. Occasionally, however, it becomes bogged down for many iterations in the vicinity of a poor quality resolution before moving on to a much superior optimum fit. We investigate this behavior in a simulation study and suggest ways of overcoming the obstacles it presents.
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    Journal of Chemometrics 8 (1994), S. 205-219 
    ISSN: 0886-9383
    Keywords: Fractional factorial design ; Significant effects ; ANOVA ; Probability plotting ; Bayes plot ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This paper presents a method for identifying significant effects in fractional factorial designs. The method is based on comparing functions of the estimated effects with a scale invariant reference distribution. The method is illustrated and compared with alternative techniques on a dataset from processed cheese production. The method corresponded well to other methods (probability plotting and Bayes plot) that do not make use of error estimates. These methods were better than F-tests with few (two or four) degrees of freedom for error.
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    Journal of Chemometrics 8 (1994) 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 245-261 
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    Keywords: Factor analysis ; Spectral resolution ; Two-dimensional luminescence ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A factor analysis algorithm that estimates the spectra of mixture components using the set of most dissimilar rows and/or columns is described and illustrated. This algorithm uses the distance as a measure of spectral similarity and is suitable for application to a variety of the bilinear matrix-formatted data types produced by hyphenated and multidimensional analytical techniqes. The algorithm requires that the data matrix contain at least one row or column that corresponds to the pure spectrum of each component to effect accurate spectral resolution. The performance of the method is illustrated using the resolution of excitation and emission spectra of up to four components from experimental fluorescence excitation-emission matrices (EEMs). In the case of the EEM, characteristic bands in an emission spectrum effect resolution of the excitation spectrum of the corresponding component, while characteristic bands in an excitation spectrum lead to resolution of the corresponding emission spectrum. The use of the set of most dissimilar rows and columns to evaluate the degree of overlap in the component spectra and compare the quality of row and column solutions is also described.
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    Journal of Chemometrics 8 (1994), S. 293-294 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 295-296 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 303-303 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 373-373 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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    Journal of Chemometrics 8 (1994), S. 445-446 
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    Keywords: Chemistry ; Analytical Chemistry and Spectroscopy
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  • 63
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Biotechnology and Bioengineering 5 (1963), S. 309-330 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Biological purification of water pollutants depends upon a complex balance of organisms and environment conducive to effective metabolism. The bench scale test is useful to determine effects of a given waste water on that balance and to suggest controls promoting optimum purification. Applicability of laboratory results depends, in part, upon an experimental design similating anticipated operating conditions. This paper discusses advantages and limitations of historical bench-tests as a guide for design of tests giving data that are more useful during full-scale operation.
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    Biotechnology and Bioengineering 5 (1963) 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Notes: A 50-gal. growth chamber is described together with its air filter and humidifier. The unit was designed especially for the production of Neurospora crassa, and was found to be effective in producing bulk amounts of mycelia with a high specific activity of tryptophan synthetase.
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    Biotechnology and Bioengineering 5 (1963), S. 87-89 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Notes: Addition of the S-2-hydroxyethyl-, S-2-chloroethyl-, S-n-propyl-, and S-iso-propyl-derivatives of homocysteine, and methoxinine to S. aureofaciens (ATCC 13900) fermentations resulted in production of 7-chloro-6-demethyltetracycline in addition to the normally synthesized 7-chlortetracycline.
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    Biotechnology and Bioengineering 5 (1963), S. 123-129 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method of inoculating nutrient surfaces uniformly with bacterial cells has been developed. The method is based on controlled exposure of samples in a humidified chamber to a spray produced from a bacterial suspension. Factors affecting uniformity of inoculation (ionic strength of suspension, force of spray, distance between spray nozzle and sample, and exposure time) were studied in detail. Under optimum condition using agar medium in Petri plates, differences between total counts for six plates inoculated simultaneously, or between counts for individual 2 cm.2 areas taken at any location on any of the plates, were not statistically significant at the 5% level. The coefficient of variability for counts on 2 cm.2 areas renged from 8 to 12% between tests of 216 counts each.
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    Biotechnology and Bioengineering 5 (1963) 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Biotechnology and Bioengineering 5 (1963), S. 185-192 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By growing Aspergillus parasiticus (C.M.I. 15957) under controlled conditions on sterilized peanuts an average of 265 mg. of aflatoxin per kilogram of peanuts has been produced and subsequently isolated. Other strains from the A. flavus-oryzae group gave lower yields of aflatoxin and one such strain gave aflatoxin from which certain normal components were absent. The aflatoxin produced on sterilized peanuts by any particular strain of A. flavus-oryzae was shown by thin-layer chromatography to contain the same major components as were produced by that strain on unsterilized whole peanuts.
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    Biotechnology and Bioengineering 5 (1963), S. 221-230 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A process has been developed giving over-all yields of about 50%: which could be increased to about 80% with higher material costs and processing time. The preferred method of recovering nucleotides from the cytoplasm has been thermal extraction by means of a heat exchanger followed by filtration, protein precipitation, and carbon adsorption. The concentrated eluate from the carbon is absorbed onto Dowex 1 ion-exchange resin, and groups of nucleotides are removed by pH-defined eluents and recovered by a second carbon adsorption. Finally, standard ion-exchange resolutions have been used to recover individual nucleotides. Other biochemicals in the extract have been investigated, and preliminary work has been done on the combination of nucleotide extraction with the recovery of nucleic acids from the residual cells.
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    Biotechnology and Bioengineering 5 (1963), S. 231-242 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the present paper the authors described laboratory fermentors used in the Antibiotics Research Institute since 1958 for research concerning the technology of the biosynthesis of antibiotics and amino acids and other aerobic fermentations. The lids of the fermentors are made from stainless steel, the vessels are made from glass. The fermentors are placed, always four each, in eight water baths with automatic temperature regulation within a range of ±0.5°C. Details regarding construction, auxiliary equipment, and working procedures used for the sterilization of fermentors and media, inoculation, injection of additives, and defoaming are given. The set-up for one-stage and multi-stage, batch and continuous cultivation are discussed.
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    Biotechnology and Bioengineering 24 (1982), S. 797-804 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Recently, considerable interest has been shown in the study and analysis of immobilized cell reactors. One of the major uses of such a reactor system is expected to be in ethanol production from carbohydrates. One distinct disadvantage of this system is carbon dioxide gas holdup associated with unsteady-state temperature distribution across the reactor. Taking into account the earlier published data and assuming steady-state-substrate balance, and unsteady-state energy balance, and an average gas holdup of 20% with the heat retained by the gas neglected, the average reaction rate in the differential element was computed. Finally, a mathematical model to predict steady-state temperature profile along the reactor was developed. It was verified with experimental data obtained from an immobilized yeast reactor column (1 m × 14.5 cm). The experimental data fit well those computed from the model within an accuracy of 5%.
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    Biotechnology and Bioengineering 24 (1982), S. 837-845 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Notes: Alcohol dehydrogenase has been immobilized to the basic copolymer and its several derivatives using various techniques. Enzyme coupling to the supports with amino groups by means of glutaraldehyde was found the most suitable. Activity of alcohol dehydrogenase coupled to these amino supports was comparable to that of the enzyme bound to Sepharose. Thermal and pH stability of alcohol dehydrogenase increased essentially upon immobilization. Kinetic properties of the immobilized enzyme differed from those of free alcohol dehydrogenase, pH optimum shifted to alkaline range, and apparent Michaelis constants for substrates and coenzymes increased. Curvatures observed in Lineweaver-Burk plots for coenzymes suggest an involvement of diffusion effects in the reaction catalyzed by alcohol dehydrogenase linked to these polymers.
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    Biotechnology and Bioengineering 24 (1982), S. 871-887 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The acid precipitation of soya protein was studied in a continuous-flow tubular reactor under conditions of turbulent flow. Preliminary batchwise experiments of a semiquantitative nature were also carried out on a bench-scale reactor to better define the parameters affecting precipitate growth. The experiments indicated the dominant growth mechanism to be the aggregation of primary precipitate particles produced by the contacting of the protein and acid streams. The rate of particle growth was observed to rise with an increase in the protein concentration as well as with greater intensity of turbulence. The final mean particle size decreased with increased intensity of turbulence. A theoretical model was set up to simulate the growth of the precipitate particles.
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    Biotechnology and Bioengineering 24 (1982), S. 763-780 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
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    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A number of studies on packed-bed immobilized enzyme reactors have shown the significant influence of the external film mass transfer resistance on the apparent kinetic parameters. Some of the earlier mathematical models using approximation techniques have attempted to explain the linearity of the S0x vs ln (1 - x) plots observed experimentally for systems obeying Michaelis-Menten kinetics. However, there has been no critical examination of the bounds of validity of the approximations used. Further, the situations where the above linearity is not valid have been examined neither conceptually nor quantitatively. The work presented here overcomes these drawbacks of the earlier analyses by approaching the problem from a different angle. Methods of evaluation of the intrinsic kinetic parameters under different experimental situations have been outlined and illustrated with several examples.
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    Biotechnology and Bioengineering 24 (1982), S. 903-918 
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    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Wood chips from bigtooth aspen (Populus grandidentata Michx.) were saccharified by reaction with liquid hydrogen fluoride either anhydrous or containing up to 10% v/v water. The reaction products were separated into a solid lignin fraction and a water-soluble saccharide fraction. The fluoride content of the lignin (determined after alkaline fusion) was initially about 1 mg/g wood, but was lowered to 0.1 mg/g wood by grinding and washing. Thus little or no chemical binding of fluoride to lignin occurred during hydrogen fluoride (HF) solvolysis. Analysis of the water-soluble fraction by gel filtration on Biogel P2 columns showed a range of low-molecular-weight oligosaccharides and only 10-20% sugar monomers. Thus considerable reversion occurred during HF evacuation. Posthydrolysis conditions were optimized for these reversion products by varying temperature and acid concentration. Optimal conditions at 1 h were 140°C with 100mN sulfuric acid or 225mN Hydrofluoric acid resulting in monomer yields of 〉 90% for 0.5% sugar solutions and 〉 80% for 10% sugar solutions. After reaction of pure cellulose (Filter paper) with hydrogen fluoride in the absence of water, and terminating the reaction with calcium carbonate, the reaction intermediate α-D-glucopyranosylfluoride was isolated with a maximal yield of 0.2 g/g paper. Upon purification via paper chromatography glucosylfluoride was identified by its specific rotation and also by gas chromatography-mass spectrometry of its tetra-O-trimethylsilyl derivative.
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    Biotechnology and Bioengineering 24 (1982), S. 971-975 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Glycerol dehydrogenase was immobilized in polyacrylamide gel layered over a small platinum screen and used to catalyze the oxidation of glycerol. In the presence of NAD+ and potassium ferricyanide, the coupling reaction generated a measurable electrical potential which was found to be Nernstian with respect to the glycerol concentration range of 10-4M to 10-1M. The reproducibility of the measurement and the optimal conditions for glycerol determination were described.
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    Biotechnology and Bioengineering 24 (1982), S. 983-989 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982), S. 1007-1013 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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  • 81
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    Biotechnology and Bioengineering 24 (1982), S. 1093-1103 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The metabolic regulation of tylosin synthesis by Streptomyces fradiae NRRL 2702 was studied in batch and chemostat cultures using a soluble synthetic medium. In batch culture a medium which diminished the trophophase-idiophase kinetic pattern was used to assess the activities of the enzymes involved in tylosin synthesis. The enzymes methylmalonyl-coenzyme A carboxyltransferase (EC 2.1.3.1) and propionyl-coenzyme A carboxylase (EC 6.4.1.3) showed early enzymatic derepression, both enzymes reaching their highest specific activities after 72-96 fermentation. The activity of macrocin 3′ -O-methyltransferase, the enzyme catalyzing the conversion of macrocin (tylosin C) to tylosin (tylosin A). also peaked at 72 h. The specific activities of the three enzymes showed close correlation with the qtylosin value. In chemostat cultures the activities of the enzymes and the intracellular level of the adenylate pool and energy charge were studied as a function of dilution rate. Under steady-state conditions, increases in the specific growth rate repressed the enzymes activities with a concomitant increase in the intracellular level of the adenylate pool, while the adenylate energy charge remained almost constant and in the range 0.5-0.52. The highest specific activities of the enzymes were observed when D = 0.008 h -1. The specific rate of tylosin synthesis was inversely proportional to the specific growth rate and the intracellular level of adenylate pool. The pool of adenylate could be a nutritional parameter which had a considerable influence on the biosynthesis of tylosin.
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  • 82
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    Biotechnology and Bioengineering 24 (1982), S. 1135-1144 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Rates of hydraulic transport of water, solute permeabilities, and sieving coefficients of homogeneous κ-carrageenan and bovine serum albumin membranes were measured. These values increased with the water content of membranes. The data show good agreement with the predictions based on the pore model.
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  • 83
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    Biotechnology and Bioengineering 24 (1982), S. 1155-1163 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Saccharomyces cerevisiae NRRL Y-2034, S, uvarum NRRL Y-1347, and Zymomonas mobilis NRRL B-806 each were separately immobilized in a Ca-alginate matrix and incubated in the presence of a free-flowing and continuous 1, 3, 5, 10, or 20% (w/w) glucose solution. In general, the yeast cells, converted 100percnt; of the 1, 3, and 5% glucose to alcohol within 48 h and maintained such a conversion rate for at least two weeks. The bacterium converted ca. 90% (w/w) of the 1, 3, and 5% glucose to alcohol continuously for one week. However, both the yeast and bacterium were inhibited in the highest glucose (20% w/w) solution. All of the immobilized cultures produced some alcohol for at least 14 days. Immobilized S. cerevisiae was the best alcohol producer of all of the glucose concentrations; the yeast yielded 4.7 g ethanol/100 g solution within 72 h in the 10% glucose solution. After 7-8 days in the 10% solution, S. cerevisiae produced ethanol at 100% of theoretical yield (5.0 g ethanol/100 g solution), with a gradual decrease in alcohol production by 14 days. Immobillized S. uvarum produced a maximum of 4.0 g ethanol/100 g solution within 2 days and then declined to ca. 1.0 g ethanol/100 g solution after 7 days continuous fermentation in the 10% glucose solution. Zymomonas mobilis reached its maximum ethanol production at 4 days (4.7 g/100 g solution), and then diminished similarly to S. uvarum. The development of a multiple disk shaft eliminated the problem both of uneven distribution of alginate-encapsulated cells and of glucose channeling within the continuous-flow fermentor column. This invention improved alcohol production about threefold for the yeast cells.
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  • 84
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    Biotechnology and Bioengineering 24 (1982), S. 1341-1370 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Development of a unified model of biofilm-reactor kinetics is based on substrate-utilization kinetics, mass transport, biofilm growth, and reactor analysis. The model is applied to steady-state conditions for complete-mix, fixed-bed, and fluidized-bed reactors with and without recycle. The results of modeling experiments demonstrate that simple loading factors and kinetic relationships are insufficient to describe the performance of a variety of biofilm processes. Instead, the interactions among utilization kinetics, biofilm growth, and reactor configuration determine the performance. For example, fluidized-bed reactors can achieve superior performance to complete-mix and fixed-bed reactors because the biofilm is evenly distributed throughout the reactor while the liquid regime has plug-flow characteristics. When it is possible, experimental results which demonstrate key concepts are presented.
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    Biotechnology and Bioengineering 24 (1982), S. 1371-1387 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A poly(acrylic acid)-polyethylene graft copolymer was prepared and used initially to couple to acid phosphatase, using soluble carbodiimides. Yields which were quite good were obtained with CMC but not with EDAC. The copolymers was used to couple trypsin using EEDQ. Several organic solvents were investigated for the preparation of the “activated” poly(acrylic acid) intermediate. Using the activated system, high concentrations of trypsin were bound but the relative activities were not very high. The yield was good with bovine serum albumin (BSA). When the method was used for invertase, acid phosphatase, and alkaline phosphatase, the yields were poor and the copolymer was shown to absorb protein by an ion-exchange mechanism. However, the activated system gave a good yield of coupling to phenylpropylamine. A polyethylene-coacrylic-acid polymer containing 13% of acrylic acid (by weight) was then converted to the acid chloride by refluxing with thionyl chloride. The chlorinated copolymer which contained 0.7% chlorine and a thionyl-chloride-treated polyethylene control which contained no chlorine were investigated in immobilization studies. Such coupling involved bovine serum albumin (BSA), alkaline phosphatase, trypsin, β-galactosidase, and invertase. Bovine serum albumin coupled well to the support, but none of the enzymes gave high levels of enzymes activity. Phenylpropylamine coupled well and all of the acid chloride groups were involved. Tyrosine reacted with 63% of the available acid chloride groups.
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    Biotechnology and Bioengineering 24 (1982), S. 1403-1418 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A mathematical model is presented which describes the growth of two bacterial species in mixed chemostat cultures under dual substrate limitation. Competition experiments between a facultatively chemolithotrophic Thiobacillus and either a heterotroph or an obligately chemolithotrophic Thiobacillus served as an experimental model system [Gottschal, de Vries, and Kuenen, Archives of Microbiology, 121, 241-249 (1979)]. Furthermore, the introduction of Monod-type growth kinetics in the model allowed an assessment of the relative importance of the growth parameters for the outcome of the competition. In addition, it is shown how the results of the mathematical description of the two-membered mixed cultures can be used to predict the outcome of the competition between the three species competing for the two growth-limiting substrates acetate and thiosulfate in a three-membered mixed culture. In contrast to the experimental data of Gottschal, de Vries, and Kuenen it is predicted that two of the three species or only one of them (the “mixotroph”) will survive in the culture. Within the framework of the proposed mathematical model, two possible explanations for the experimentally observed coexistence of three species are suggested: either the very slow dynamics of the system did not allow the attainment of a true steady state within the time scale of the present experiments or some parameters describing the mixed culture were extremely sensitive towards minor fluctuations in dilution rate. The results of the present mathematical model support the view that facultatively chemolithotrophic bacteria are able to survive under appropriate limiting mixed substrate conditions in the presence of more “specialized” heterotrophs and obligately chemolitotrophs, in spite of their relatively low specific growth rate.
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    Biotechnology and Bioengineering 24 (1982), S. 1461-1463 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982), S. 1469-1472 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
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    Biotechnology and Bioengineering 24 (1982), S. 1495-1505 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The feasibility of a continuous compression milling pretreatment process for the enzymatic hydrolysis of lignocellulosics has been demonstrated. Pretreatment efficiency was improved significantly by adjustment of feedstock moisture content prior to milling and/or increasing the roll pressure on the feedstock. Optimum moisture contents for newspaper (24%). corn stover (17%), popular (12-20%) were determined. Sugar Yields of 48% were obtained from air-dried newspaper after six passes through even-pressure rolls and the specific energy input was 0.21kW h/lb. The Effect of roll speed on enzymatic hydrolysis improvement was constant over a roll speed range of from 30-110 ft/min (65 rpm). Enzymatic hydrolysis results from commercial-scale pretreatment of moist newspaper processed at 6 tons/h/ correlated well with laboratory mill data while energy consumption was 26% less.
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    Biotechnology and Bioengineering 24 (1982), S. 1877-1880 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982), S. 1827-1838 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The objectives of this research were to investigate the growth of immobilized yeast cells in k-carrageenan gel and study the effect of trapping hydroxyapatite (tricalcium phosphate) crystals into the matrix. Using k-carrageenan, the final number of cells per milliliter of gel is at least an order of magnitude higher than free cells per milliliter of medium. A “cell retention” theory explaining this cell concentration difference was proposed. Coexistence of yeast cells and an additional agent such as tricalcium phosphate results in sustained viability through internal pH control, increased cell loading, greater settling velocity, and enhanced ethanol production.
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    Biotechnology and Bioengineering 24 (1982), S. 1813-1826 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Monod's kinetic model was used to correlate the specific growth rate of mixed activated sludge with the limiting substrate of phosphorus for both batch and continuous-flow culture systems. In the batch reactor system, the specific growth rate varied from 0.092 to 0.617 h-1 and the saturation constant changed from 25.5 to 117.5 when the COD: P ratio was controlled within the range of 10 to 788 and at the temperature 25± 0.5°C. An inverse relationship between specific growth rate and cell yield was found. the maximum specific growth rate and the saturation constant obtained from this study were equal to 0.64 h-1 and 0.378mg/L, respectively. In the completely mixed continuous-flow culture system, it was found that the substrate utilization, biological solids production, and sludge composition were markedly affected by the source of phosphorus available in the wastewater. The phosphorus-limited activated sludge is normally high in carbohydrate content and low in protein content. Also, sludge organisms growth under the severely restricted phosphorus condition usually possess a large capsule. These capsulated carbohydrate-like substances can be converted to cellular protein if the source of phosphorus is added. The values of cell yield in the continuous-flow activated sludge system are predictable by the use of kinetic constants that are generated from batch culture studies.
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    Biotechnology and Bioengineering 24 (1982), S. 1851-1869 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Based on the experimental investigations with H. polymorpha and Methylomonas M 15 in bench-scale airlift tower-loop reactors, a general distributed parameter model was developed and used to simulate to cultivation process in a 40-m-high production reactor. This general model was simplified with regard to the gas phase and loop balances and was employed to optimize cell productivity and/or profit in a 20-m-high pilot-plant airlift tower-loop reactor. Maximum cell productivity always occurs in the oxygen-transfer-limited growth range. In case of a high “penalty factor” for nonconsumed substrate, maximum profit is attained at the boundary between substrate and oxygen-transfer-limited growth. Oxygen-transfer limitation exists in the lower half of the tower, whereas in the upper half, substrate limitation prevails. The longitudinal dissolved oxygen concentration passes a minimum in this case as has been determined experimentally in the bench-scale column. The simulation results agree fairly well with the data measured in the pilot plant.
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    Biotechnology and Bioengineering 24 (1982), S. 1889-1896 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982), S. 1965-1974 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A four-step strategy is presented which allows the establishment of plant cell cultures producing high yields of secondary plant products. The application of suitable methods (radioimmunoassay, fluorescence screening) for the selection of overproducing differentiated plants and cell colonies is stressed. By precursor feeding and hormone application, plant cell cultures can greatly be influenced in their production behavior. A highly sensitive, selective regulatory mechanism for the uptake and storage of alkaloids in Catharanthus vacuoles is demonstrated. Overproducing variant cell strains are so far the most promising tool for the future biotechnological application of the plant cell culture method.
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    Biotechnology and Bioengineering 24 (1982), S. 2013-2030 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A new mathematical model is presented model is presented for use in the design and optimization of fluidized-bed fermenters. Unlike previous models, the biomass particle size is not a required input parameter, but is predicted as a consequence of the process by which the fermenter reaches a steady state. Both tower fermenters and supported-film bioreactors are included in the analysis. The differences between them are explained as a consequence of the different effects of added biomass on the particle settling velocity and the tendency of a fluidized bed to stratify. A detailed qualitative treatment of solids mixing allows the model to predict the varying biomass concentration through a tower fermenter and the more constant concentration in the supported film reactor. Other features of this analysis are the inclusion of an axial dispersion term to allow for different liquid mixing conditions, and the introduction of a variable transformation that eliminates the need for a computer solution. A sample design problem is included.
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    Biotechnology and Bioengineering 24 (1982), S. 2063-2076 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Refiner mechanical pulp was biologically treated with several higher fungi in order to test their potential for increasing the strength of paper. It was among the white-rot fungi that the best results were obtained. Polyporus versicolor gave the best overall improvement in handsheet properties with no reduction in tear. The strength improvement is due to attack on lignin and to an increase in fiber flexibility as measured by water retention values and by acidic group content of the treated pulps. The brown-rot fungi had a detrimental effect on paper properties.
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    Biotechnology and Bioengineering 24 (1982), S. 2109-2113 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982) 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
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    Biotechnology and Bioengineering 24 (1982), S. 2175-2188 
    ISSN: 0006-3592
    Keywords: Chemistry ; Biochemistry and Biotechnology
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Stereospecific hydrolysis of insoluble monoesters by lipases are reported. Among the lipases tested, porcine pancreatic lipase was the most stereospecific when acting on 3-chloro-2-methyl propanol propionate. When the chain length of the acid was enhanced, the stereospecificity decreased. Initial rate measurements analysis concluded that the observed stereospecificity was the result of different catalytic constants rather than different Michaelis constants. From these results, methods were derived for the preparation of l- or d-3-chloro-2-methylpropanol (an intermediary in the synthesis of levomepromasine) based on the hydrolysis of esters by soluble or immobilized lipases.
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