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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    Journal of Chemometrics 4 (1990), S. 47-50 
    ISSN: 0886-9383
    Keywords: Classification ; Pattern recognition ; Preprocessing ; Chemistry ; Analytical Chemistry and Spectroscopy
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Over the past 15 years the linear learning machine has been applied to a large number of chemical problems. The learning machine approach is conceptually simple and does not require knowledge about the statistical distribution of the data. However, there are problems associated with this approach. One problem which has not been investigated is the influence of mislabeled samples on the positioning of the hyperplane in feature space. If a few samples in a data set are incorrectly tagged prior to training (i.e. the samples are labeled as members of class 2 even though they are actually members of class 1), it is still possible using the linear learning machine to achieve a classification success rate of 100% for the training set. However, unfavorable results will be obtained for the prediction set. The magnitude of this effect and its potential implications regarding the proper use of the linear learning machine are discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 34 (1996), S. 3061-3069 
    ISSN: 0887-624X
    Keywords: aggregation ; emulusion polymerization ; flocculation ; latex ; particles ; polymer ; size distribution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The basic features of a three-step experimental process to produce supermicron polymer particles are described. First, a submicron emulsifier-free latex is prepared by a well-known technique. Second, the latex is aggregated by destabilizing with cetyl pyridinium chloride under constant stirring conditions, to yield roughly spherical clusters of 6-12 μ diameter. Third, the aggregates are stabilized with poly(vinyl alcohol) and internally coalesced by heating at or above the glass transition temperature. The final product particles have relatively smooth surfaces. Results are qualitatively interpreted in terms of a dynamic equilibrium where the aggregate size is determined by a balance between attractive interparticle potentials and stirring shear forces. Bimodal aggregate size distributions suggest the aggregate break-up mechanism may involve the erosion of individual latex particles and small fragments from the surface of aggregates. © 1996 John Wiley & Sons, Inc.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 35 (1997), S. 447-453 
    ISSN: 0887-624X
    Keywords: polyether ; polyester ; aryl ether ; nucleophilic substitution ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Arene-iron chemistry was applied in the synthesis of a novel liquid crystalline polymer. The chemistry, which is based on iron cyclopentadienyl (FeCp) arene complexes, allows sequential nucleophilic substitution of the chlorides from 1,3-dichlorobenzene-FeCp complex and photolytic decomplexation of the products to afford asymmetrical aryl ethers. This methodology provides easy access to novel polyether-esters, and is potentially useful in the synthesis of various functional polyarylates. © 1997 John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Bognor Regis [u.a.] : Wiley-Blackwell
    Journal of Polymer Science Part A: Polymer Chemistry 33 (1995), S. 1597-1606 
    ISSN: 0887-624X
    Keywords: emulsion polymerization ; surfactants ; oligomers ; Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: It is well known that the amount of surfactant must be carefully controlled during starve-fed emulsion polymerization processes. Too little surfactant leads to emulsion instability and coagulation, while too much surfactant leads to secondary particle formation. Although these relationships are qualitatively understood in the art, there is little quantitative basis to guide the synthetic chemist, especially in multistep starve-fed emulsion polymerization processes to make larger supermicron particles. We have developed a method, which will be described in a companion article, to control the surfactant level by monitoring the surface tension during polymerization. In order to quantitatively predict how much surfactant to add at any given time, one needs to know in advance the adsorption characteristics of the soap. Further complicating the matter is the formation of “in situ” or oligomeric surfactant during polymerization with aqueous initiators such as ammonium persulfate.This work demonstrates how to prepare surface-active oligomers and how to make latex particles using them as surfactant. First, we established the mass balance for the initiator-derived sulfate groups in seed latexes by conductometric, potentiometric, and iodometric titrations. Based on the characterization of seed latexes, a method for determining the effective sulfate concentration has been developed. When surface-active oligomers were used as the only surfactant, we obtained a series of monodisperse, supermicron copolymer latex particles with diameters up to 3.22 μm. This is a similar result to that obtained with a commercially made anionic surfactant. © 1995 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    ISSN: 0887-624X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Changing solvent has a dramatic effect on the outcome of HPC stabilized dispersion polymerization of styrene in polar solvents. In methoxyethanol/ethanol mixtures, particle size varies from essentially infinity for unstabilized reactions (below 30% ethanol) to about 3 microns in ethanol. In a series of n-alcohols, there was a maximum in particle size at intermediate chain length: particle size increased from 2 microns in methanol to 8.3 microns in pentanol, then decreased again to 1 micron in octadecanol. These results were rationalized in terms of the three-component Hansen solubility parameters. The largest particles were obtained in solvents with Hanson polarity and hydrogen bonding terms closest to HPC. The generality of the three-component solubility parameter approach was examined by reactions performed in eight mixed solvents with the same values of all three Hansen terms. Seven of the eight solvents gave particles of similar size and molecular weight. The two critical effects of solvent on both particle size and molecular weight appear to be: (a) the solubility properties of the grafted HPC-PS formed, and (b) the partitioning of monomer and initiator between solution and particle phases subsequent to nucleation.
    Additional Material: 12 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 11 (1994), S. 457-462 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Studies have been performed to characterize the flow of certain powders of pharmaceutical interest from a vibrating spatula. Lactose, cromolyn sodium, sodium chloride and charcoal powders were prepared by milling or sieving. Jet milling yielded micronized powder (1-10 μm), which was recovered from the product jar or metal cyclone. Particles in the larger size ranges were prepared by sieving. Photomicrograph images of the products were obtained by scanning electron microscopy. All of the powders were subjected to flow studies from vibrating beds to a top loading pan balance. Cumulative mass versus time, flow profiles were plotted. Bulk flow properties, as reflected in mass flow rates (Mi), were assessed. Irregular flow patterns were obtained for lactose, cromolyn sodium and charcoal, whereas sodium chloride was free flowing. The lengths of the lines depicting cumulative mass versus time, for samples of each material, were estimated using the inswing structured walk technique. Stride lengths (γ) of 1-100 mm were employed. Fractal dimensions were obtained from graphs of the logarithm of the cumulative mass versus time line length plotted against the logarithm of the stride length. Thus, flow irregularities were indicated by fractal dimensions (δ).In all of the powders studied, mass flow rates increased as the particle size increased. Sodium chloride did not exhibit fractal behavior (δ ≤ 1.007), as there were no flow irregularities. Lactose, cromolyn sodium and charcoal did not appear to exhibit fractal behavior (δ ≤ 1.010) at large stride lengths (γ = 15-100 mm). At small stride lengths (γ = 1-10 mm) these materials did exhibit fractal behavior (δ equals; 1.029-1.059) indicative of flow irregularity. This method may be used to numerically quantify uniformity of flow from a vibrating spatula, and would be useful in a number of industrial processes.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 12 (1995), S. 68-74 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An overview of Electro-Magnetic Tomography (EMT) using mutual inductance measurements is presented. The paper reviews the technique and principle of operation and gives a description of three case studies, which cover some of the generic design considerations and which illustrate the potential variety for inductive EMT systems. Results from the systems are described. These systems are presently experimental and possible future developments and applications are discussed.
    Additional Material: 8 Ill.
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    Weinheim : Wiley-Blackwell
    Particle and Particle Systems Characterization 9 (1992), S. 9-18 
    ISSN: 0934-0866
    Keywords: Chemistry ; Industrial Chemistry and Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Two dimensional images are often used as a basic for calculating shape descriptors of particles. An edge roughness descriptor, the fractal dimension, can be found from a Richardson plot of measured perimeter versus the measuring step length. Data Scatter on these plots is shown to be related to the incipient formation of polygonal harmonics, which are regular polygons formed during a structured walk around the image edge. This relationship was verified using both computer generated fractal images and real particle outlines.
    Additional Material: 14 Ill.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    Chichester : Wiley-Blackwell
    Journal of Physical Organic Chemistry 11 (1998), S. 787-792 
    ISSN: 0894-3230
    Keywords: nucleophilic aromatic substitution ; Meisenheimer complexes ; nucleophilic reactivity ; trinitro-aromatics ; Chemistry ; Theoretical, Physical and Computational Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: Kinetic and equilibrium results are reported for the reactions of sulphite with the ethyl and phenyl ethers of 2,4,6-trinitrophenol and 2,4,6-trinitrothiophenol in 80/20 (v/v) water/DMSO. In each case 1:1 and 1:2 adducts are observed by reaction of sulphite at one or two unsubstituted ring positions respectively. In the case of the ethyl derivatives these adducts are long-lived however, the phenyl derivatives rapidly yield 2,4,6-trinitrobenzenesulphonate, the substitution product. This difference is attributed to a change in the nature of the rate-determining step, from nucleophilic attack with the phenyl derivatives to leaving group departure with the alkyl derivatives. © 1998 John Wiley & Sons, Ltd.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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