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  • 1
    ISSN: 1476-5535
    Keywords: Penicillin V acylase ; Beijerinckia indica var.penicillanicum ; Mutation ; Solvent effect
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Summary Beijerinckia indica var.penicillanicum mutant UREMS-5, producing 168% more penicillin V acylase, was obtained by successive treatment with UV, γ-irradiation and ethylmethane sulfonate. Penicillin V acylase production by the mutant strain was resistant to catabolite repression by glucose. Incorporation of glucose, sodium glutamate and vegetable oils in the medium enhanced enzyme production. The maximum specific production of penicillin V acylase was 244 IU/g dry weight of cells. Effect of solvents on hydrolysis of penicillin V by soluble penicillin V acylase and whole cells was studied. Methylene chloride, chloroform and carbon tetrachloride significantly stimulated the rate of penicillin V hydrolysis by whole cells.
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  • 2
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    Journal of industrial microbiology and biotechnology 8 (1991), S. 99-106 
    ISSN: 1476-5535
    Keywords: Mutation ; UV ; Biodegradation ; Chlorinated organic compound
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Summary In this study, a continuous-flow UV-induced mutation (CUM) device and the CUM device coupled to a selector (CUMS) reactor were fabricated and tested for their ability to enhance the probability of obtaining populations capable of chlorinated organic biodegradation. A mixed culture of bacteria were used as the starting strain for both the CUM and CUMS processes. Populations were obtained from the CUM and CUMS systems capable of 4-chlorobenzoic acid, 2,4-dichlorobenzoic acid and chlorendic acid biodegradation. Non-UV irradiated population served as controls for the experiments and did not demonstrate chlorinated organic biodegradation over the test duration.
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  • 3
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    Current genetics 18 (1990), S. 441-445 
    ISSN: 1432-0983
    Keywords: Neurospora crassa ; Mutation ; RIP phenomenon
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary In the further analysis of a cross in which the mis-sense allele, am 3, of the Neurospora crassa am (glutamate dehydrogenase) gene was present in one parent together with two ectopic wild-type gene copies, one ascus was identified in which the two ectopic copies had been inactivated by the RIP process whereas the am 3 allele continued to produce its characteristic enzyme variety in active, but heat-sensitive, form. The am 3 allele had also acquired a new HindIII restriction site. It had no detectable methylation. The mutations responsible respectively for the new restriction site and the modified enzyme properties were separated from each other, and from the original am 3 mutation, by selecting for intragenic recombination on either side of the am 3 site. In this way two new effectively wild-type alleles were generated, one characterised by its heat-sensitive and kinetically modified enzyme product and the other by a new HindIII site. These results demonstrate that the RIP phenomenon can be a source of new functional alleles.
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  • 4
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    Journal of molecular evolution 19 (1983), S. 214-218 
    ISSN: 1432-1432
    Keywords: Codon: anticodon adaptation ; Mutation ; Selection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Synonymous codon usage frequencies, derived from cDNA clone sequences, were compared for several sets of vertebrate genes. Gene sets as diverse as those expressed in avian skeletal muscle and in mammalian liver showed similar patterns of synonymous codon usage. There were no significant differences suggesting tissue-specific co-adaptation of codon usage patterns and tRNA anticodon profiles. The results indicate a consensus codon usage pattern for vertebrate genes which is largely independent of taxonomic class, tissue of expression, and the cellular fate and rate of evolution of the encoded proteins. Certain elements of the consensus codon usage pattern indicate that it is the product of natural selection and not simply a mutational equilibrium among phenotypically equivalent synonyms.
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  • 5
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    Journal of molecular evolution 35 (1992), S. 156-180 
    ISSN: 1432-1432
    Keywords: DNA damage ; DNA repair ; Chromatin ; Evolution ; Nucleosomes ; Nuclear matrix ; Active genes ; Z-DNA ; Sperm ; Mutation ; Molecular clock
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Some evolutionary consequences of different rates and trends in DNA damage and repair are explained. Different types of DNA damaging agents cause nonrandom lesions along the DNA. The type of DNA sequence motifs to be preferentially attacked depends upon the chemical or physical nature of the assaulting agent and the DNA base composition. Higher-order chromatin structure, the nonrandom nucleosome positioning along the DNA, the absence of nucleosomes from the promoter regions of active genes, curved DNA, the presence of sequence-specific binding proteins, and the torsional strain on the DNA induced by an increased transcriptional activity all are expected to affect rates of damage of individual genes. Furthermore, potential Z-DNA, H-DNA, slippage, and cruciform structures in the regulatory region of some genes or in other genomic loci induced by torsional strain on the DNA are more prone to modification by genotoxic agents. A specific actively transcribed gene may be preferentially damaged over nontranscribed genes only in specific cell types that maintain this gene in active chromatin fractions because of (1) its decondensed chromatin structure, (2) torsional strain in its DNA, (3) absence of nucleosomes from its regulatory region, and (4) altered nucleosome structure in its coding sequence due to the presence of modified histones and HMG proteins. The situation in this regard of germ cell lineages is, of course, the only one to intervene in evolution. Most lesions in DNA such as those caused by UV or DNA alkylating agents tend to diminish the GC content of genomes. Thus, DNA sequences not bound by selective constraints, such as pseudogenes, will show an increase in their AT content during evolution as evidenced by experimental observations. On the other hand, transcriptionally active parts may be repaired at rates higher than inactive parts of the genome, and proliferating cells may display higher repair activities than quiescent cells. This might arise from a tight coupling of the repair process with both transcription and replication, all these processes taking place on the nuclear matrix. Repair activities differ greatly among species, and there is a good correlation between life span and repair among mammals. It is predicted that genes that are transcriptionally active in germ-cell lineages have a lower mutation rate than bulk DNA, a circumstance that is expected to be reflected in evolution. Exception to this rule might be genes containing potential Z-DNA, H-DNA, or cruciform structures in their coding or regulatory regions that appear to be refractory to repair. This study supports the molecular clock hypothesis when applied to one gene within a group of related species and contends that evolutionary rates might vary between genes and gene segments not only as a result of differences in selective constraints but also as a result of differences in the rate of damage minus rate of repair among different segments of chromatin DNA.
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  • 6
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    Journal of molecular evolution 39 (1994), S. 448-451 
    ISSN: 1432-1432
    Keywords: Synonymous substitution ; Escherichia coli ; Salmonella typhimurium ; Mutation ; Recombination ; Selection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The spatial distribution of synonymous substitutions in enterobacterial genes is investigated. It is shown that synonymous substitutions are significantly clustered in such a way that a synonymous substitution in one codon elevates the rate of synonymous substitution in an adjacent codon by about 10%. The level of clustering does not appear to be related to the level of gene expression, and it is restricted to a range of two or three codons. There are at least three possible explanations: (1) sequence-directed mutagenesis, (2) recombination, and (3) selection.
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  • 7
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    Plant cell reports 13 (1994), S. 372-376 
    ISSN: 1432-203X
    Keywords: Asparagus officinalis L ; Habituation ; Mutation ; Somatic embryogenesis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Somatic embryogenesis from different genotypes of Asparagus officinalis L. could be obtained by in vitro culture of shoot apices. Apices were first cultured on an auxin-rich inducing medium and then transferred onto a hormone-free development medium. All genotypes tested in this way produced a few somatic embryos. In some experiments, during the development phase, a new kind of friable highly embryogenic tissue appeared in a random manner. These tissues could be continuously subcultured on a hormone-free medium and were named embryogenic lines. Five of these embryogenic lines regenerated plants from somatic embryos. These regenerated plants exhibited an increased embryogenic response compared to the parent plants; e.g. apex culture produced somatic embryos without any auxin treatments. For one of the embryogenic lines, a genetic analysis showed that the improved embryogenic response of regenerated plants was controlled by a mendelian dominant monogenic mutation.
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  • 8
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    Current genetics 26 (1994), S. 281-284 
    ISSN: 1432-0983
    Keywords: Ofloxacin ; Mitochondria ; Mutation ; Recombination ; Topoisomerase ; Yeast
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Ofloxacin, a specific inhibitor of bacterial topoisomerase II, is known to inhibit the growth of yeast cells and to induce rho − mutants in the yeast S. cerevisiae. The frequency of ofloxacin-induced petite mutants under non-growth conditions was found to be strongly diminished when the cells were depleted in intramitochondrial ATP. Under optimal conditions of mitochondrial mutagenesis the drug induced mitotic recombination and reverse mutation in diploid strains but failed to cure either killer plasmids or the 2 μm DNA of dividing cells. The sensitivity to ofloxacin of the strains deficient in the DNA strandbreak repair pathway (rad52) was significantly higher then that of the wild-type strains and of the mutants deficient in excision or mutagenic DNA repair. The results are compatible with the idea that the cytotoxic and genetic activity of ofloxacin in yeast probably results from the inhibited DNA ligation function of topoisomerase II creating DNA breaks that are reparable through the recombination repair pathway.
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  • 9
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    Environmental management 8 (1984), S. 309-324 
    ISSN: 1432-1009
    Keywords: Animals ; Indicators ; Air pollution ; Ecosystem responses
    Source: Springer Online Journal Archives 1860-2000
    Topics: Energy, Environment Protection, Nuclear Power Engineering
    Notes: Abstract With existing and proposed air-quality regulations, ecological disasters resulting from air emissions such as those observed at Copperhill, Tennessee, and Sudbury, Ontario, are unlikely. Current air-quality standards, however, may not protect ecosystems from subacute and chronic exposure to air emissions. The encouragement of the use of coal for energy production and the development of the fossil-fuel industries, including oil shales, tar sands, and coal liquification, point to an increase and spread of fossil-fuel emissions and the potential to influence a number of natural ecosystems. This paper reviews the reported responses of ecosystems to air-borne pollutants and discusses the use of animals as indicators of ecosystem responses to these pollutants. Animal species and populations can act as important indicators of biotic and abiotic responses of aquatic and terrestrial ecosystems. These responses can indicate long-term trends in ecosystem health and productivity, chemical cycling, genetics, and regulation. For short-term trends, fish and wildlife also serve as monitors of changes in community structure, signaling food-web contamination, as well as providing a measure of ecosystem vitality. Information is presented to show not only the importance of animals as indicators of ecosystem responses to air-quality degradation, but also their value as air-pollution indices, that is, as air-quality-related values (AQRV), required in current air-pollution regulation.
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  • 10
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    Current genetics 23 (1993), S. 430-434 
    ISSN: 1432-0983
    Keywords: S. cerevisiae ; Mutational homozygosis ; Loss of heterozygosity ; Mutation ; Recombination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A leucine-requiring hybrid of Saccharomyces cerevisiae, homoallelic at the LEU1 locus (leu1–12/leu1–12) and heterozygous for three chromosome-VII genetic markers distal to the LEU1 locus, was employed to inquire: (1) whether spontaneous gene mutation and mitotic segregation of heterozygous markers occur in positive nonrandom association and (2) whether homozygous LEU1/LEU1 mutant diploids are generated. The results demonstrate that gene mutation of leu1–12 to LEU1 and mitotic segregation of heterozygous chromosome-VII markers occur in strong positive nonrandom association, suggesting that the stimulatory DNA lesion is both mutagenic and recombinogenic. In addition, genetic analysis of diploid Leu+ revertants revealed that approximately 3% of mutations of leu1–12 to LEU1 result in LEU1/LEU1 homozygotes. Red-white sectored Leu+ colonies exhibit genotypes that implicate postreplicational chromatid breakage and exchange near the site of leu1–12 reversion, chromosome loss, and subsequent restitution of diploidy, in the sequence of events leading to mutational homozygosis. By analogy, diploid cell populations can yield variants homozygous for novel recessive gene mutations at biologically significant rates. Mutational homozygosis may be relevant to both carcinogenesis and the evolution of asexual diploid organisms.
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  • 11
    ISSN: 1432-0983
    Keywords: Thymidylate auxotrophy ; Mutation ; Recombination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A diploid yeast thymidylate auxotroph was grown under conditions of thymidylate stress ranging from depletion to excess levels of the nucleotide. High concentrations of thymidylate were mutagenic and recombinagenic whereas starvation for thymine nucleotides was recombinagenic and only slightly mutagenic. These results are discussed in relation to possible mutagenic and recombinagenic mechanisms of nucleotide pool imbalances.
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  • 12
    ISSN: 1432-072X
    Keywords: Fatty acids ; Mortierella alpina ; ω3-Desaturation ; Mutation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A mutant considered to be defective in the conversion of n-6 to n-3 fatty acids (ω3-desaturation) was derived from a Δ5-desaturation-defective mutant (Mut44) of Mortierella alpina 1S-4, after treating its spores with N-methyl-N′-nitro-N-nitrosoguanidine. This mutant cannot produce 8(Z),11(Z),14(Z),17(Z)-eicosatetraenoic acid or any other n-3 fatty acids, of which about 10% was found in its parental strain upon cultivation at 12°C. The mutant's growth rate was comparable to that of the parental strain when grown at 28°C, but it became much slower when the mutant grew at 12°C, at which the lag phase for Mut44 was about 2 d but 5 d for the mutant.
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  • 13
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    Archives of microbiology 124 (1980), S. 143-148 
    ISSN: 1432-072X
    Keywords: Anacystis ; Blue-green algae ; Cyanobacteria ; Mutation ; Pigments ; Red light ; Synecaococcus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Under far-red (〉650 nm) illumination Anacystis nidulans grows poorly and develops a low chlorophyll content. During continued culture over many generations there are increases in growth rate and in the chlorophyll/phycocyanin ratio, usually occurring in concomitant and stepwise fashion. From such selection cultures six clones have been established which differ from the parent in pigment content and show improved growth rate in far-red light. From the evidence at hand the six clones are presumed to be spontaneous mutants selected under the photosynthetically restrictive condition of far-red illumination.
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  • 14
    ISSN: 1432-072X
    Keywords: Temperature ; Mutation ; Thermotolerance ; Escherichia coli ; Salmonella typhimurium ; Pseudomonas aeruginosoa ; DNA gyrase ; gyrA ; Nalidixic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract A prolonged incubation of Escherichia, Salmonella or Pseudomonas at 48°C with nalidixic acid selected mutants (T48) able to grow at 48°C. A prolonged incubation at 54°C of the T48 mutants selected mutants (T54) able to grow at 54°C. These mutants were susceptible to the same bacteriophages as the original mesophilic strains. Auxotrophic phenotypes of Escherichia coli and Salmonella typhimurium mesophilic parents were demonstrated by these mutants if they were cultivated on minimal agar with cellobiose at 48°C or 54°C or on a minimal agar with glucose at 37°C. The T48 alleles mapped in the gyrA region of E. coli or S. typhimurium chromosome. In S. typhimurium the T54 alleles, which permit growth at 54°C, were shown by cotransductional analysis to be linked to gyrA.
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  • 15
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    Archives of microbiology 159 (1993), S. 98-100 
    ISSN: 1432-072X
    Keywords: Prophage induction ; Weigle reactivation ; Mutation ; Filamentation ; Nitrofurantoin ; Vibrio cholerae el tor
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Treatment of Vibrio cholerae el tor strain SLH22(J) with nitrofurantoin induced dose-dependent prophage ‘kappa’, the maximum induction being 6-fold the spontaneous induction level. UV-inactivated ‘kappa’ phages were Weigle reactivated, the maximum Weigle factor being 1.8 and 2.0 respectively in nitrofurantoin and UV pretreated el tor strain H218 Smr. Nitrofurantoin treatment also caused significant filamentation of the el tor strain H218 Smr and mutation of these cells from ampicillin sensitivity to ampicillin resistance. The levels of the four SOS-like responses induced by this drug were low but significant.
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  • 16
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    Journal of mathematical biology 33 (1994), S. 111-137 
    ISSN: 1432-1416
    Keywords: B-cells ; Immune system ; Idiotypic networks ; Mutation ; Replicator equations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract In order to evaluate the role of idiotypic networks in the operation of the immune system a number of mathematical models have been formulated. Here we examine a class of B-cell models in which cell proliferation is governed by a non-negative, unimodal, symmetric response function f(h), where the field h summarizes the effect of the network on a single clone. We show that by transforming into relative concentrations, the B-cell network equations can be brought into a form that closely resembles the replicator equation. We then show that when the total number of clones in a network is conserved, the dynamics of the network can be represented by the dynamics of a replicator equation. The number of equilibria and their stability are then characterized using methods developed for the study of second-order replicator equations. Analogies with standard Lotka-Volterra equations are also indicated. A particularly interesting result of our analysis is the fact that even though the immune network equations are not second-order, the number and stability of their equilibria can be obtained by a superposition of second-order replicator systems. As a consequence, the problem of finding all of the equilibrium points of the nonlinear network equations can be reduced to solving linear equations.
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  • 17
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    Journal of mathematical biology 30 (1992), S. 597-632 
    ISSN: 1432-1416
    Keywords: Autocatalysis ; Mutation ; Perturbation theory ; Qualitative analysis ; Replication dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract A class of kinetic equations describing catalysed and template induced replication, and mutation is introduced. This ODE in its most general form is split into two vector fields, a replication and a mutation field. The mutation field is considered as a perturbation of the replicator equation. The perturbation expansion is a Taylor series in a mutation parameter λ. First, second and higher order contributions are computed by means of the conventional Rayleigh-Schrödinger approach. Qualitative shifts in the positions of rest points and limit cycles on the boundary of the physically meaningful part of concentration space are predicted from flow topologies. The results of the topological analysis are summarized in two theorems which turned out to be useful in applications: the rest point migration theorem (RPM) and the limit cycle migration theorem (LCM). Quantitative expressions for the shifts of rest points are computed directly from the perturbation expansion. The concept is applied to a collection of selected examples from biophysical chemistry and biology.
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  • 18
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    The journal of membrane biology 139 (1994), S. 203-212 
    ISSN: 1432-1424
    Keywords: Mg2+ current ; Mutation ; Paramecium ; Intracellular Mg2+ homeostasis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract “Eccentric” is a newly-isolated mutant of Paramecium tetraurelia that fails to swim backwards in response to Mg2+. In the wild type, this backward swimming results from Mg2+ influx via a Mg2+-specific ion conductance (I Mg. Voltage-clamp analysis confirmed that, as suspected, step changes in membrane potential over a physiological range fail to elicit I Mg from eccentric. Further electrophysiological investigation revealed a number of additional ion-current defects in eccentric: (i) The Ca2+ current activated upon depolarization inactivates more slowly in eccentric than in the wild type, and it requires longer to recover from this inactivation. (ii) The Ca2+-dependent Na+ current deactivates significantly faster in the mutant, (iii) The two K+ currents observed upon hyperpolarization are reduced by 〉60% in eccentric. It is difficult to envision how these varied pleiotropic effects could result from loss of a single ion current. Rather, they suggest that the eccentric mutation affects a global regulatory system. Two plausible hypotheses are discussed.
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  • 19
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    Journal of mathematical biology 12 (1981), S. 355-362 
    ISSN: 1432-1416
    Keywords: Branching process ; Mutation ; Extinction ; Progeny size
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract A branching process method is employed to study the survival probability of a slightly advantageous mutant gene with a general distribution of progeny size in a large population. A counter-example to a classic proposition is given. A somewhat weaker result is proved.
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  • 20
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    Journal of mathematical biology 30 (1992), S. 597-631 
    ISSN: 1432-1416
    Keywords: Autocatalysis ; Mutation ; Perturbation theory ; Qualitative analysis ; Replication dynamics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract A class of kinetic equations describing catalysed and template induced replication, and mutation is introduced. This ODE in its most general form is split into two vector fields, a replication and a mutation field. The mutation field is considered as a perturbation of the replicator equation. The perturbation expansion is a Taylor series in a mutation parameter λ. First, second and higher order contributions are computed by means of the conventional Rayleigh-Schrödinger approach. Qualitative shifts in the positions of rest points and limit cycles on the boundary of the physically meaningful part of concentration space are predicted from flow topologies. The results of the topological analysis are summarized in two theorems which turned out to be useful in applications: the rest point migration theorem (RPM) and the limit cycle migration theorem (LCM). Quantitative expressions for the shifts of rest points are computed directly from the perturbation expansion. The concept is applied to a collection of selected examples from biophysical chemistry and biology.
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  • 21
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    Journal of mathematical biology 31 (1993), S. 123-132 
    ISSN: 1432-1416
    Keywords: Genealogy ; Coalescent ; Mutation ; Migration ; Markov chain
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract The genealogical process of neutral genes with mutation in geographically structured populations is investigated. Following Watterson [24], the sampled genes are partitioned into two types, old equivalence classes and new equivalence classes. The model is described by a bivariate continuous time Markov chain as an interactive particle system. Some results are obtained in the two-population model and the stepping stone model with symmetric nearest-neighbour migration.
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  • 22
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    Journal of mathematical biology 13 (1981), S. 95-104 
    ISSN: 1432-1416
    Keywords: Stochastic migration ; Island model ; Mutation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract Recurrence relations are derived for stochastic migration in the island model with a finite number of subpopulations. Two models are considered, one involving a constant probability that each individual breeding in a given colony has migrated from another, the other assuming the exchange of fixed numbers of migrants between colonies each generation. The equilibrium solutions are expressed in terms of two measures of genetic differentiation among subpopulations, one similar to Nei's measure of genetic distance, and the other closely related to the coefficient of kinship. Both measures are shown to be necessary for a complete description of population structure. The predictions of the models of stochastic migration are compared with the corresponding classical model of deterministic migration.
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  • 23
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    Journal of mathematical biology 32 (1993), S. 33-44 
    ISSN: 1432-1416
    Keywords: Mutation ; Selection ; Random drift ; Muller's ratchet
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract Two independently derived theories predict upper limits to the mutation rate beyond which evolution cannot be controlled by natural selection. One is the theory of Muller's ratchet, explaining the low phylogenetic age of parthenogenetic clones, the other one is the theory of error thresholds, predicting the maximal information content of selfreplicating molecules in prebiotic evolution. Both theories are based on similiar mathematical models but reach qualitatively different conclusions. Muller's ratchet only works in finite populations, while error thresholds are a deterministic phenomenon. In this paper it is shown that this discrepancy is due to different assumptions about the fitness values the selfreplicative units are allowed to assume. If no lower limit for the fitness values is assumed then the deterministic equilibrium frequency of the currently best genotype is strictly positive, no matter how strong mutation is, and random drift is required to cause its extinction (Muller's ratchet). On the other hand, positive lower limits for the fitness values lead to zero equilibrium frequencies in the deterministic description provided the mutation rate is high enough and no back mutations occur.
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  • 24
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    Journal of mathematical biology 32 (1994), S. 193-218 
    ISSN: 1432-1416
    Keywords: Selection ; Mutation ; Mutation load ; Quantitative genetic traits
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract Haldane (1937) showed that the reduction of equilibrium mean fitness in an infinite population due to recurrent deleterious mutations depends only on the mutation rate but not on the harmfulness of mutants. His analysis, as well as more recent ones (cf. Crow 1970), ignored back mutation. The purpose of the present paper is to extend these results to arbitrary mutation patterns among alleles and to quantitative genetic traits. We derive first-order approximations for the equilibrium mean fitness (and the mutation load) and determine the order of the error term. For a metric trait under mutation-stabilizing-selection balance our result differs qualitatively from that of Crow and Kimura (1964), whose analysis is based on a Gaussian assumption. Our general approach also yields a mathematical proof that the variance under the usual mutation-stabilizing-selection model is, to first order, µ/s (the house-of-cards approximation) as µ/s tends to zero. This holds for arbitrary mutant distributions and does not require that the population mean coincide with the optimum. We show how the mutant distribution determines the order of the error term, and thus the accuracy of the house-of-cards approximation. Upper and lower bounds to the equilibrium variance are derived that deviate only to second order as µ/s tends to zero. The multilocus case is treated under the assumption of global linkage equilibrium.
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  • 25
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    Journal of mathematical biology 30 (1991), S. 199-213 
    ISSN: 1432-1416
    Keywords: Polygenic dynamics ; Quantitative trait ; Selection ; Mutation ; Cumulants ; Generating function
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Mathematics
    Notes: Abstract A new approach for describing the evolution of polygenic traits subject to selection and mutation is presented. Differential equations for the change of cumulants of the allelic frequency distribution at a particular locus and for the cumulants of the distributions of genotypic and phenotypic values are derived. The derivation is based on the assumptions of random mating, no sex differences, absence of random drift, additive gene action, linkage equilibrium, and Hardy-Weinberg proportions. Cumulants are a set of parameters that, like moments, describe the shape of a probability density. Compared with moments, however, they have properties that make them a much more convenient tool for investigating polygenic traits. Applications to directional and stabilizing selection are given.
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  • 26
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    Theoretical and applied genetics 65 (1983), S. 41-46 
    ISSN: 1432-2242
    Keywords: Triticum aestivum ; Wheat ; Protein ; Mutation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Poor adaptability or functional quality of much germplasm used for breeding high-protein hard red winter wheats prompted mutagenesis as an alternative means of increasing grain protein content. Four hard red winter wheat genotypes — KS644 (‘Triumph// Concho/Triumph’), ‘Kaw’, ‘Parker’, and ‘Shawnee’ — were treated with 0.40 M ethyl methanesulfonate (EMS). Advanced lines (M8-M10) were selected that had a 3-year mean grain protein advantage of 0.7% to 2.0% over controls. Increased grain protein content was generally associated with decreased grain yield and kernel weight, but some high-protein mutant lines had yields or kernel weights similar to those of original genotypes. Changes in height and lodging induced by EMS were generally favorable, most mutants being shorter and lodging less than controls, but blooming date was generally delayed, a deleterious change. One line also changed from resistant to segregating for wheat soil-borne mosaic virus. Mutant lines might be utilized in cross-breeding programs, particularly if negative pleiotropic effects and linkages are absent.
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  • 27
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    Theoretical and applied genetics 65 (1983), S. 225-230 
    ISSN: 1432-2242
    Keywords: Tissue culture ; Mutation ; Sequential mutations ; Rice ; Oryza sativa L.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Four mutations for early heading, albina, short culm and sterility were obtained in the progenies of twelve rice plants regenerated from a single callus of a rice seed. Studies on the segregation rates of these mutations revealed that for each mutation a single recessive gene was likely to be involved and that there was no linkage among the genes. The segregation pattern also showed that these mutations were induced in the following sequence: early heading, albina, and short culm and sterility during the stage of callus growth until the beginning of the regeneration of the rice plants.
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  • 28
    ISSN: 1432-2242
    Keywords: Mutation ; Normalizing-selection ; Lethal-equivalence ; Genetic-load ; Neutral-theory
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Through a series of genetic load studies made on 1) samples of Drosophila willistoni from two sites in Mesitas, Colombia, it was found that the relative contributions to the total, subvital and lethal loads reflect lethal equivalences (B/A) ratios which support more the balancing theory of population structure than the neutralist theory. Moreover, measurements of population size have revealed the existance of very small demes in local populations. Under such conditions we have calculated extremely small lethal equivalence ratios in demes where probably a great deal of consanguinity takes place. We are aware that under these conditions B/A ratios cannot be very good monitors of random load measurements and, therefore, suggest a change in the mathematical formulation that take into consideration the existance of small populations. Furthermore, it appears plausible that the degree of penetrance in the heterozygous condition changes as the population structure changes. We speculate that natural populations may have unknown selective mechanisms capable of guiding unknown dominance modifiers according to the intensity of selection.
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  • 29
    ISSN: 1432-2242
    Keywords: Interchange ; Chromosome polymorphism ; Mutation ; Selection ; Equilibrium ; Rye
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary A persistent chromosomal polymorphism exists in a population of cultivated rye, Secale cereale (Candela et al. 1979). In order to ascertain the possible causes that maintain it, we have estimated the fitness values of structurally homozygous and heterozygous plants and the mutation rate of spontaneous interchange. The estimates of the selection coefficient against heterozygotes (s=0.15-0.40) and of the mutation rate u=6.12×10−2 support a mutation-selection equilibrium as a likely cause of the interchange chromosome polymorphism.
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  • 30
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    Theoretical and applied genetics 67 (1984), S. 203-205 
    ISSN: 1432-2242
    Keywords: Ethyl methanesulphonate ; Mutation ; Myo-inositol ; Nicotiana tabacum, tobacco
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Summary Tobacco seeds treated with ethyl methanesulphonate produces mutations as well as physiological growth debility. The addition of myo-inositol to seeds undergoing mutagenic treatment stimulated growth and increased survival of subsequent plants with negligible effect on the mutation frequency.
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  • 31
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    Theoretical and applied genetics 87 (1994), S. 657-667 
    ISSN: 1432-2242
    Keywords: Transposable elements ; Mutation ; Evolution ; DNA repair ; Gene conversion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The mobile DNAs of the Mutator system of maize (Zea mays) are exceptional both in structure and diversity. So far, six subfamilies of Mu elements have been discovered; all Mu elements share highly conserved terminal inverted repeats (TIRs), but each sub-family is defined by internal sequences that are apparently unrelated to the internal sequences of any other Mu subfamily. The Mu1/Mu2 subfamily of elements was created by the acquisition of a portion of a standard maize gene (termed MRS-A) within two Mu TIRs. Beside the unusually long (185–359 bp) and diverse TIRs found on all of these elements, other direct and inverted repeats are often found either within the central portion of a Mu element or within a TIR. Our computer analyses have shown that sequence duplications (mostly short direct repeats interrupted by a few base pairs) are common in non-autonomous members of the Mutator, Ac/Ds, and Spm(En) systems. These duplications are often tightly associated with the element-internal end of the TIRs. Comparisons of Mu element sequences have indicated that they share more terminal components than previously reported; all subfamilies have at least the most terminal 215 bp, at one end or the other, of the 359-bp Mu5 TIR. These data suggest that many Mu element subfamilies were generated from a parental element that had termini like those of Mu5. With the Mu5 TIRs as a standard, it was possible to determine that elements like Mu4 could have had their unusual TIRs created through a three-step process involving (1) addition of sequences to interrupt one TIR, (2) formation of a stem-loop structure by one strand of the element, and (3) a subsequent DNA repair/gene conversion event that duplicated the insertion(s) within the other TIR. A similar repair/conversion extending from a TIR stem into loop DNA could explain the additional inverted repeat sequences added to the internal ends of the Mu4 and Mu7 TIRs. This same basic mechanism was found to be capable of generating new Mu element subfamilies. After endonucleolytic attack of the loop within the stem-loop structure, repair/conversion of the gap could occur as an intermolecular event to generate novel internal sequences and, therefore, a new Mu element subfamily. Evidence supporting and expanding this model of new Mu element subfamily creation was identified in the sequence of MRS-A.
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  • 32
    ISSN: 1617-4623
    Keywords: Rice ; Tetraploid irradiation ; Genome rearrangement ; rDNA ; Mutation
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract The organization of tandemly repeated sequences of ribosomal DNA (rDNA) in rice mutants derived from γ-irradiated tetraploids was analyzed. Southern hybridization analysis of nuclear DNA revealed that most of the intergenic spacers (IGSs) in mutant rDNA are replaced concertedly by new molecular species. The new IGSs are produced by the amplification of a subrepeat of about 250 bp. Results obtained from sequence analyses indicate that various intermediate molecular species of the subrepeat were formed during structuring of the IGS region and that many rearrangements occurred between them. These findings demonstrate the effectiveness of recurrent irradiation of tetraploids for inducing artificial genome rearrangement, and also indicate the extreme plasticity and variability of genome structure in plants.
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  • 33
    ISSN: 1617-4623
    Keywords: TOL plasmid ; Biodegradation ; Pseudornonas putida ; Evolution ; Mutation
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    Topics: Biology
    Notes: Abstract TOL plasmid pWW0 from Pseudomonas putida mt-2 encodes catabolic enzymes required for the oxidation of toluene and xylenes. The structural genes for these catabolic enzymes are clustered into two operons, the xylCMABN operon, which encodes a set of enzymes required for the transformation of toluene/xylenes to benzoate/toluates, and the xylXYZLTEGFJQKIH operon, which encodes a set of enzymes required for the transformation of benzoate/toluates to Krebs cycle intermediates. The latter operon can be divided physically and functionally into two parts, the xylXYZL cluster, which is involved in the transformation of benzoate/toluates to (methyl)catechols, and the xylTEGFJQKIH cluster, which is involved in the transformation of (methyl)catechols to Krebs cycle intermediates. Genes isofunctional to xylXYZL are present in Acinetobacter calcoaceticus, and constitute a benzoate-degradative pathway, while xylTEGFJQKIH homologous encoding enzymes of a methylphenol-degradative pathway and a naphthalene-degradative pathway are present on plasmid pVI150 from P. putida CF600, and on plasmid NAH7 from P. putida PpG7, respectively. Comparison of the nucleotide sequences of the xylXYZLTEGFJQKIH genes with other isofunctional genes suggested that the xylTEGFJQKIH genes on the TOL plasmid diverged from these homologues 20 to 50 million years ago, while the xylXYZL genes diverged from the A. calcoaceticus homologues 100 to 200 million years ago. In codons where amino acids are not conserved, the substitution rate in the third base was higher than that in synonymous codons. This result was interpreted as indicating that both single and multiple nucleotide substitutions contributed to the amino acid-substituting mutations, and hence to enzyme evolution. This observation seems to be general because mammalian globin genes exhibit the same tendency.
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  • 34
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Aromatic acid isomers ; Low capacity ion-exchange resin ; Microbore packed columns
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A low-capacity, anion-exchange, porous-polymer resin was used as the packing material in a microbore column. Using a phosphate buffer containing various organic modifiers, retention behavior of substituted benzoic acid isomers with amino, chloro, methyl, nitro and carboxylic groups was investigated. The effect of ethanol, acetonitrile and sodium dodecylsulfate used as organic modifiers on the retention behavior at various eluent pH values was studies and optimum separations of the positional isomers reported.
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  • 35
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    Chromatographia 18 (1984), S. 668-672 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Mixed eluents ; Preferential sorption of eluents ; Pressure effects
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    Topics: Chemistry and Pharmacology
    Notes: Summary Pronounced base line perturbations were repeatably observed in LC both in alternating recycling and in backflushing experiments when binary eluents and refractometric detectors were used. The perturbations which we call eigenzones appeared immediately after operating the recycling or the backflushing valve, and their size and shape depended on the nature of both the column filling and the mixed mobile phase as well as on the pressure drop across the column. Experimental results presented confirm that the primary causes of the eigenzones were the pressure changes in the columns which influenced the sorption equilibrium of mixed eluent components within the column packing. Some practical consequences of this effect are briefly discussed.
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  • 36
    ISSN: 1612-1112
    Keywords: Polycyclic aromatic hydrocarbons ; Column liquid chromatography ; Polyphenyl bonded phases ; Retention and carbon content
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    Topics: Chemistry and Pharmacology
    Notes: Summary The relationship between the retention of PAHs having various molecular sizes and the carbon contents (%) of bonded stationary phases with various types of ligands were investigated. The examined stationary phases were phenyl, diphenyl, triphenyl and benzyl-bonded silicas. The data indicated that sometimes it is not true that the retention of any solute relates linearly to the carbon content of the stationary phase. As the result, it is suggested that the pore size distribution of the silica support, the bulkiness of the ligand bonded to the silica and the molecular size of solute should also be considered before any precise statement can be made.
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  • 37
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    Chromatographia 18 (1984), S. 175-182 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fourier transform IR ; Polar compounds ; Coal products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Fourier-transform infrared spectrometry (FTIR) was utilized as a detection system for high-performance liquid chromatography of polar compounds on a normal bonded-phase system. In addition to FTIR, UV (254 nm) and refractive index detection were employed in the separation of model compounds containing oxygen and nitrogen atoms in their molecules (phenols, alcohols, neutral and weakly basic nitrogen compounds). A polar amino-cyano (PAC) bonded-phase column was employed with a binary mobile phase (98:2 CDCl3:CH3CN). The separations and the information gained from each detector is discussed, including interactions between sample material and mobile phase. A polar fraction of a coal-derived product is also chromatographed under identical conditions. The results based on FTIR detection and chromatographic retention behavior suggest the exclusive presence of hindered and unhindered phenols.
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  • 38
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    Chromatographia 18 (1984), S. 211-215 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Alkylbenzenes ; PAHs ; Retention prediction ; Microcomputer
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    Topics: Chemistry and Pharmacology
    Notes: Summary The microcomputer-assisted retention prediction system in C18 reversed-phase HPLC is described. The system is based on the use of the hydrophobic parameter and the correlation factor of alkylbenzenes and polycyclic aromatic hydrocarbons (PAHs) which are highly correlated to their retention in reversed-phase HPLC. The system is evaluated by comparing the retention data between measured and predicted values. One of the typical examples applied for PAH analysis in the extracts of diesel particulate matter shows the high potential of the system investigated.
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  • 39
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    Chromatographia 18 (1984), S. 216-220 
    ISSN: 1612-1112
    Keywords: Cation exchangers ; Column liquid chromatography ; Exchange capacity, determination ; Organic peroxidation
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    Topics: Chemistry and Pharmacology
    Notes: Summary Two oxidation procedures for the synthesis of silicabased aliphatic sulfonic acid cation-exchangers for HPLC are described. Several reaction conditions for oxidizing a terminal-bonded thiol with organic peroxides are provided along with their yields, capacities, reproducibility, and chromatographic behavior. Also, three methods for determining exchange capacity are discussed, and their relationship to the capacity factors of charged solutes is compared. The maximum capacity determined by the titration of the bonded silica was 0.34 meq/gram. The general problems of synthesizing cation-exchangers, measuring their efficiencies and exchange capacities, and evaluating their overall performances are outlined.
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  • 40
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    Chromatographia 18 (1984), S. 369-373 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion exchange ; dynamic ; Metal ions ; Equilibria effects
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    Topics: Chemistry and Pharmacology
    Notes: Summary Equilibria occurring during the dynamic ion exchange separation of metal ions were examined, and their effect on the chromatography of the metal ions was evaluated. Bonded reversed-phase silica, pure organic reversed phase, and silica columns were used to differentiate between the role of silica and the reverse phase. The results show that system peaks had the most important influence on the applicability of dynamic exchangers to quantitative metal ion determinations. The response of system peaks to sample composition (pH, ionic strength, matrix effects) was complicated and could not be predicted easily. Equilibria effects that can cause analytical errors were identified and recommendations for elimination of such errors are given.
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  • 41
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amines ; Phenols ; Fourier transform I.R.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Several chromatographic parameters have been examined as to their effect on detectability for microbore high-performance liquid chromatography coupled with Fourier-transform infrared spectrometry. Detection limits for several compound classes are presented as amount injected. Improvements in detectability for this technique are discussed.
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  • 42
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polystyrene packings ; Pre-column derivatization ; Thiamine compounds ; UV and fluorescence detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The chromatography of thiochrome and related phosphate esters was studied on two different polystyrene packing materials. The adsorbents were compared with respect to capacity factors, plate heights and resolution factors measured with different mixtures of phosphate buffer (pH 8.5) and methanol. In contrast with derivatized silica, these phases were found to be stable using an alkaline mobile phase and sample. Fast separations were possible with good peak symmetry at all organic modifier concentrations.
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  • 43
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    Chromatographia 18 (1984), S. 445-448 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amino-bonded stationary phase ; Ion-exchange ; Fermentation solution ; Biomass
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary In this work the analytical separation of biomass hydrolysis and fermentation products is described. Aminobonded phase and ion exchange materials (HPX 87H, HPX 42A, μ Spherogel Carbohydrate) were used as HPLC stationary phases for the determination of monomeric and oligomeric carbohydrates, carbohydrate degradation and fermentation products. The HPX 42A and the amino-bonded phase columns are especially suitable for the analysis of the gluco oligomers. The HPX 87H column separates the monomeric sugars and their degradation and fermentation products (e.g. furfurals and ethanol) very well. Using the μ Spherogel Carbohydrate column the lower gluco-oligomers as well as the monomeric sugars and their degradation and fermentation products, can be determined within 35 minutes.
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  • 44
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral bonded phase ; Racemate resolution
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    Topics: Chemistry and Pharmacology
    Notes: Summary A chiral stationary phase with an immobilized, optically active diamine was prepared for the separation of enantiomers. The synthesis of the phase was carried out by bonding (−)trans-1,2-cyclohexanediamine to microparticulate silica gel through the coupling agent 3-glycidoxypropylsilane. The resolution of the racemic compounds catechin, 2,2′-dihydroxy-1,1′binaphthyl and trans-1,2-cyclohexandiol, is reported.
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  • 45
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    Chromatographia 18 (1984), S. 495-498 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; PAHs ; Molecular shape recognition
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    Topics: Chemistry and Pharmacology
    Notes: Summary The molecular-shape recognition of polycyclic aromatic hydrocarbons has been studied on various stationary phases in reversed-phase high-performance liquid chromatography. The examined stationary phases were phenyl-, diphenyl-, triphenyl- and benzyl-bonded silicas. The results of regression analysis inidcated that triphenylsilica is the best packing material to recognize the difference in the molecular-shape of structural isomers. This fact was confirmed by the separation of 4-ring isomers.
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  • 46
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Retention data ; Substituted benzene derivatives ; Correlations
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    Topics: Chemistry and Pharmacology
    Notes: Summary The capacity factors of substituted benzene derivatives on bonded phases of various chain lengths in the reversed-phase mode have been measured and correlation of retention data between four stationary phases has been investigated by linear regression analysis. As a result, a difference in the retention mechanism between phases of shorter chain length and octadecylsilica was observed. In addition, it is also apparent that the multicombination treatment between retention data and descriptors such as π, HA, HD and σ promises the possibility of predicting the retention of substituted benzene derivatives on various reversed-phase stationary phases.
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  • 47
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polyamines ; Dansyl derivatives ; Peak compression
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    Topics: Chemistry and Pharmacology
    Notes: Summary Analytical conditions for the high-speed, reversed-phase, liquid chromatographic of a diamine (putrescine) and polyamines (spermine and spermidine) were determined. Various elution modes were employed using the same mobile phase constituents: 20mM sodium heptane sulfonate and 20mM acetic acid as solvent A and, pure acetonitrile as solvent B. Samples were derivatized with dansyl chloride before injection. Under isocratic conditions, the separation of the three polyamines was achieved in 7 min. The use of a linear elution gradient led to the same analytical time but with a better resolution of the putrescine peak from non-polyamine frontal peaks. For these measurements, the sample size was 5μl. This volume was increased to 20μl and the use of a steep gradient combined with the peak-compression technique allowed a fast analysis in 2–3 minutes, which may be compared with a 30 min run time necessary when a conventional column is used.
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  • 48
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Bovine milk ; Multivariate optimization ; Glycerophospholipids ; Molecular species separation ; Chemometrics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The molecular species profile, representing the fatty acid combinations on the glycerol backbone, is the most fundamental description of an intact glycerophospholipid class and provides a key to understanding its functional characteristics. We have developed a powerful RP-HPLC method for the separation of molecular species, including so-called “critical pairs”, of natural mixtures of 1,2-diacyl-sn-glycero-3-phosphocholine 1,2-diacyl-sn-glycero-3-phosphoethanolamine from bovine milk and other natural sources. We have used a novel multivariate development and optimization strategy to locate the region of optimum separation conditions within a prechosen domain of the chromatographic parameter space.
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  • 49
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Open tubular columns ; Cross-linked polyacrylate stationary phase ; Photopolymerization ; Antracene derivatives
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    Topics: Chemistry and Pharmacology
    Notes: Summary Polyacrylate films containing a lauryl moiety were fabricated on about 12 μm I.D. fused silica capillaries by in-situ photopolymerization of acrylates. Relatively thick films up to 1 μm were obtained by the technique. The films were tested as retentive layers for reversed phase open tubular liquid chromatography (OTLC). Due to the presence of the incorporated lauryl moiety in the layer considerable retention could be achieved for polar compounds with aqueous mobile phases. The efficiency of the prepared columns approximates to the theoretical value. The polyacrylate films appear to be extremely stable even under strong basic conditions. The films swell considerably in the presence of nonpolar solvents resulting in more favourable retention and a significant improvement of the chromatographic performance.
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  • 50
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    Chromatographia 35 (1993), S. 627-630 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fatty acid analysis ; Fish oils
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    Topics: Chemistry and Pharmacology
    Notes: Summary A chromatographic method has been developed for the determination of eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA) in fish oil dietary supplements containing triglycerides rich in (n−3) polyunsaturated fatty acids (PUFAs). Following the ester saponification, free fatty acids were resolved by TLC into two fractions: i) a more mobile group of saturated and monounsaturated fatty acids and ii) a less mobile group containing PUFAs. The PUFA fraction was further analyzed by HPLC to determine the levels of EPA and DHA in the fish oil sample.
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  • 51
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Carbidopa and levodopa in plasma ; Electrochemical detection
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    Topics: Chemistry and Pharmacology
    Notes: Summary A validated reversed-phase high-performance liquid chromatographic procedure employing electrochemical detection (LCEC) for the analysis of carbidopa and levodopa in human plasma is reported. The method is sensitive and specific with amperometric detection at a glassy carbon working electrode with Eapp=0.75 V vs. Ag/AgCl. The retention times of levodopa, internal standard, and carbidopa are 3.3, 4.5, and 9.7 minutes, respectively, with an overall chromatographic run time of 12.0 minutes. The peak height ratio versus plasma concentration is linear over the range of 5.0 to 500 ng/mL for each analyte and exhibits correlation coefficients of 0.9957 or better (n=9). The mean absolute recovery of carbidopa and levodopa using the described assay is 36.6 and 66.0%, respectively. The inter- and intra-day accuracy and precision are within 11.8% of the actual values for all concentrations. Also, due to the demonstrated instability of carbidopa and levodopa in plasma a procedure is provided to circumvent this. Blood collected in pre-treated Vacutainer tubes can be stored in an ice bath for up to 4 hours without any significant degradation, thereby providing a practical means for processing several clinical samples simultaneously.
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  • 52
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fullerenes ; FullereneSep® ; Separation factor ; HPLC-particle beam mass spectrometry
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    Topics: Chemistry and Pharmacology
    Notes: Summary High-performance liquid chromatographic separation of fullerene mixtures in the range C60 to C100 can be achieved using a novel stationary phase which rivals the performance of the more expensive ‘Pirkle-type’ columns currently employed.
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  • 53
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    Chromatographia 35 (1993), S. 675-678 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion chromatography ; Trace metal determination ; Sample contamination ; Human hair
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The dynamic ion-exchange chromatographic analysis of bivalent ions, such as Cu, Pb, Zn, Ni, Co and Mn in resistant organic matrices needs preliminary wet ashing with oxidizing acids (HNO3 and HClO4). Such treatment may lead to an increase in the amounts of metals present in the sample due to their release from containers or equipment used in an acidic environment and to metal impurities contained in the acids. The effect of these interferences in the determination of trace metals in human hair was studied.
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  • 54
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Normal phase separations ; Cyanopropyldimethyl silica ; Chloro-added polycyclic aromatic hydrocarbons ; Environmental samples
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Retention characteristics in normal phase HPLC of highly biologically active chloro-added polycyclic aromatic hydrocarbons (PAHs) were studied. Silica, cyanopropyldimethylsilyl- and aminopropylsilyl- modified stationary phases were investigated. Retention properties of chloroadded PAHs on these phases were shown to be strongly influenced by the number of chloro-additions. This is due to the strong polarity of the methylene carbon at the chloro-addition site. Active silica had a strongly degrading effect on the unstable chloro-added PAHs during separation. Aminopropylsilica did not exhibit sufficient selectivity towards chloro-added PAHs when compared to chlorosubstituted PAHs. Cyanopropyldimethylsilica was shown to be applicable to a group separation of chloro-added and chloro-substituted PAHs. A fast clean-up procedure for chloro-added PAHs in complex samplesis outlined. It involves an initial elimination of more polar substances on a short open column with strongly deactivated silica and a subsequent separation on a cyanopropyldimethylsilyl HPLC column in normal phase mode.
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    Chromatographia 32 (1991), S. 345-349 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Column packings ; Pore size distribution ; Diffusion and adsorption ; Band broadening
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The complex intraparticle structure typical of chromatographic column packings has been analyzed by use of an equivalent network model which emphasizes pore size distribution and connectivity. Special attention is given as to the way in which diffusion and adsorption interact and display modified peak spreading characteristics according to the morphology of the pore space. This study reveals a very significant increase in the column band broadening over that expected from physical adsorption which can arise from particular distributions of pore sizes. This has implications for designing packings which take advantage of the separating power due to adsorption but do not compromise the resolution of the chromatographic system.
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  • 56
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; GC/ECD detection ; PCBs, ortho and non-ortho ; Chromatographic separation ; Congener determination ; FTIR identification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An analytical procedure for the individual determination of ortho and non-ortho PCB congeners in sediments, using high performance liquid chromatography (HPLC) preseparation and gas chromatography/ECD detection, is described. Gas chromatography/FTIR spectrometry (GC/FTIR) and gas chromatography/mass spectrometry (GC/MS) were employed for individual congener identification and determination. Sample extraction, clean-up of extract and selective elution procedures were optimized by using reference certified marine sediment samples. Recovery and precision were typically 83% and 16% respectively at 2 ng/g of total PCB content. The proposed procedure, tested by analyzing real sediment samples, showed a reproducibility better than 20% at 13 ng/g PCB level.
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  • 57
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Glutamine ; Pyroglutamic acid ; Amino acids formulations
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The aminoacid glutamine in aqueous solution and in conditions of high temperature and long term storage is partly transformed into pyroglutamic acid which exhibits potential neurotoxic effects. Commercially available aminoacid mixtures supplemented with glutamine are heat-sterilized and some losses of glutamine and formation of pyroglutamic acid may occur. The aim of the work was to set up an easy and reliable HPLC method which allows the determination of pyroglutamic acid as a degradation product of glutamine. The column was a 5 μm Hypersil ODS (100×4.6 mm) and the mobile phase 100% 0.007 M phosphate buffer pH 3.5. Stability studies in different conditions of temperature and time of storage were performed on aminoacid mixture available in the commerce.
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  • 58
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Carbonyl compounds ; Luminarin hydrazides ; Fluorescence detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Fluorogenic reagents (luminarin 3, luminarin 11 and luminarin 12), having a quinolizinocoumarin moiety as fluorophore and a carboxylic acid hydrazide function as reacting group, have been developed. These reagents were found to be highly sensitive fluorescence derivatization reagents for aldehydes and ketones in high-performance liquid chromatography. The reagents readily react with carbonyl compounds in aqueous sulphuric acid solution (0.1 M) at room temperature to produce the corresponding hydrazone derivatives, which can be separated on both reversed or normal-phase column. The structures of the derivatives were studied, together with their properties in reversed and normalphase chromatographic systems. UV absorbance, corrected fluorescence spectral data and quantum yields of luminarin 3, luminarin 11 and luminarin 12 are presented. The detection limits (signal to noise ratio=3) for aldehydes and ketones were in the sub-pmol range. Luminarin 3 was also applied to the determination of hydroxymethylfurfural (HMF) in orange juices and concentrates. The method for HMF involves the solid-liquid extraction of the juice by using a C-18 cartridge prior to derivatization and normal-phase separation of the derivative with fluorimetric detection at 387 nmex., 444 nm em. The calibration curve was linear for amounts of HMF ranging from 0.1 to 10 nmol. Intrarun relative standard deviation was 12.8% for 0.1 nmol and 2.6% for 1 nmol. Recovery studies indicated an average of 98.7±1.9% for juice concentrate and 99.8±3.2% for pasteurized juice.
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  • 59
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Method development ; Chemometrics ; Response criteria ; Analysis of drug purity
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    Topics: Chemistry and Pharmacology
    Notes: Summary Optimization procedures require adequate response criteria to assess the quality of each chromatogram obtained during the process. The objective of this paper is to evaluate the possibility of using different resolution functions, in the chromatographic separation of a drug and its impurities (particularly the impurity just eluted after the drug). This study shows the limits of some resolution expressions. The interest of the simple Δt criterion, the difference between retention times, is presented in this paper.
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  • 60
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    Chromatographia 36 (1993), S. 147-151 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polarity ; Retinoids
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    Topics: Chemistry and Pharmacology
    Notes: Summary The retention of retinoids in reversed-phase liquid chromatography was studied using aqueous mobile phases of different composition (methanol 94–86% and acetonityrile 92–82%) at five temperatures (40–60 °C). With both organic modifiers the effect of the molecular structure increased as the water content and the polarity of the mobile phase increased. The temperature-dependence increased in the same manner with aqueous acetonitrile mobile phases. The π-π interactions between the retinoids and acetonitrile diminish when the water content of the mobile phase is increased, as happens also to the hydrophobic interactions with both organic modifiers. The net effect of these changes depends on the composition of the mobile phase. There was excellent correlation of retention with all polarity parameters studied(ϕ, P′, xe, xd, xn, E T N , δT, δ, δo and δd), when the calculations were made separately with methanol and acetonitrile. The volume fraction of the organic modifier, ϕ, was the only parameter describing the retention well in both organic modifiers simultaneously.
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  • 61
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Aromatic amines ; Arylbenzylamide methylthioether derivative ; SL 85.1016 ; Pharmacokinetics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An HPLC method has been developed for the determination of SL 85.1016, a new calcium antagonist arylbenzylamide methylthioether derivative. SL 85.1016 and the internal standard, SL 87.0210, are extracted from alkaline human plasma withn-hexane and back extracted into 0.05 M phosphate buffer (pH 2.5; 0.2 ml). Acetonitrile (50 μl) is added to the final aqueous extract in order to prevent absorption of the compounds of interest onto the walls of the glass tube; this solution then is partially processed by HPLC on a C18 column with UV detection (254 nm). The determination limit of the method is 2 ng.ml−1 of SL 85.1016 in human plasma; the response to the drug is linear in the range 2–200 ng.mg−1.
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  • 62
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    Chromatographia 36 (1993), S. 347-350 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Allium ; Derivatization ; S-alk(en)yl-L-cysteine sulfoxides ; Sulfur amino acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two pre-column derivatization procedures coupled with reversed phase HPLC have been compared for the analysis ofS-Alk(en)yl0L-cysteine sulfoxides in variousAllium species. In order to establish external standards some (+/-) sulfoxides were synthesized, using a new method to enhance asymmetric synthesis of the diastereoisomers. The first derivatization method is the formation ofo-phthaldialdehyde/tert.-butylthiol derivatives which can be analyzed using UV detection. The second, presently used for amino acid analysis, is the Waters Pico-Tag method, which employs phenylisothiocyanate as derivatization reagent. As the Pico-Tag method was found to be the most efficient for determination ofS-alk(en)yl-L-cysteine sulfoxides it was used to determine the alliin content of various samples of garlic.
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  • 63
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fatty acids and bile acids ; Fluorogenic precolumn derivatization ; 2-Bromoacetyl-6-methoxynaphthalene
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    Topics: Chemistry and Pharmacology
    Notes: Summary The use of 2-bromoacetyl-6-methoxynaphthalene as a fluorogenic labelling reagent in pre-column derivatization for the HPLC separation of biologically active carboxylic acids (fatty acids and bile acids) has been investigated. The compound reacts (30 min. at 70°C) with carboxylic acids to give fluorescent esters that can be separated by reversedphase HPLC and detected at λ ex. 300 nm, λ em. 460 nm. The experimental conditions for the derivatization and chromatographic separation are discussed. Applications to the determination of valproic acid and chenodeoxycholic acid in pharmaceutical formulations are described.
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  • 64
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Valproic acid ; Simultaneous determination of anticonvulsants
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The derivatizing procedure of Moody et al. [20] for valproic acid has been simplified and applied to the simultaneous HPLC determination of valproic acid (VPA), barbital (B), primidone (PRM), phenobarbital (PB) and carbamazepine (CBZ) in serum or plasma of epileptic patients. The sample is deproteinized with acetonitrile containing esterification agents and an aliquot of the supernatant is heated to 70°C for 15 min with 4-bromophenacyl bromide. The reaction mixture is analysed on a C18 column at ambient temperature, with gradient elution and with detection at 205 nm. The time required for the chromatographic analysis is 13 min; identification is based on retention time and quantification is by peak area determination with an internal standard. The calibration curves show good linearity in the range 6.25 to 100 mg/L. The detection limits at a signal: noise ratio ≥3, ranged from 1 mg/L for B and CBZ to 2–3 mg/L for PRM, PB and VPA. The method described for the simultaneous determination of the five drugs in the same plasma pool, correlated well with isocratic HPLC methods specific for each drug. The simultaneous procedure described allows a reproducible (CVs≤6.5% within run) and rapid (25 min for sample preparation: 13 min for chromatographic run) therapeutic monitoring of patients treated with VPA and two or more antiepileptic drugs.
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  • 65
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous polymer spherical packings ; Vinyl ether ; Alkali resistance ; No abnormal adsorption
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    Topics: Chemistry and Pharmacology
    Notes: Summary Spherical, porous-polymer particles for column packing in high-performance liquid chromatography were prepared by suspension copolymerization of alkylvinyl ether with triethyleneglycol divinyl ether. The hydrophobicity of the packings was easily adjusted by changing the monomer ratio. The packings showed the usual reversed-phase liquid chromatographic properties, but did not sho abnormal retention, tailing and broadening of peaks and irreversible adsorption of ionic and aromatic substances, owing to the lack of ionic or aromatic groups. In addition, the packings were stable in alkaline solutions because of the relative alkali stability of C−O−C bonds as compared with CO−O and Si−O−C bonds in conventional packings.
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  • 66
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Anion exchange ; Indirect photometric and direct conductivity detection ; Naphthalenesulfonate ; Inorganic anions
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Indirect photometric and unsuppressed direct conductivity detection modes are examined using naphthalene mono-, di-, and tri-sulfonate as mobile phases for the separation of several anions such as F−, Cl−, NO2 −, Br−, NO3 −, SO4=,I−, and SCN− using a commercial anion exchange column. With all three mobile phases, conductivity detection shows better sensitivities and detection limits than indirect photometry. Conductivity detection is 5 to 16 times more sensitive than indirect photometry for all analytes. Detection limits achieved using these mobile phases are, for example, 0.04 ng and 0.1 ng for chloride ion with conductivity and indirect photometry, respectively. Both detection modes give wide linear ranges extending from at least 100 ppm to the detection limit of each anion which is generally about 0.02 ppm. Sulfur oxide anions such as dithionate and tetrathionate are separated using flow programming with naphthalenetrisulfonate as the mobile phase in less than 20 minutes. With both detection modes, desired chromatographic performance of these three eluents is achieved without pH adjustment of the mobile phase.
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  • 67
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Heat-treated milk ; Milk quality indicators ; 5-Hydroxymethyl-2-furfuraldehyde
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An enhanced method of HPLC for the determination of 5-Hydroxymethyl-2-furfuraldehyde (HMF) in fluid milk was perfected. Its resolving capacity permitted the specific separation of this compound. The real concentration (μmol/l) of HMF was determined and not the HMF value, as in the colorimetric analysis, where an intermediary coloured compound (HMF-TBA) is utilised. The optimum pH condition (pH=4.0–4.2) for the mobile phase to prevent overlapping between the HMF peak and the peaks of the other compound (α and β) that coeluted with the HMF and also the optimum organic solvent content (3% or 7%) were established. This is a sensitive, quick and safe method for the determination of HMF in fluid milk.
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  • 68
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chlortetracycline ; Reversed-phase silical gel ; C8 bonded phase ; Collaborative study
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An established method for the analysis of chlortetracycline by liquid chromatography using octylsilylated silica gel as the stationary phase was examined in a multicentre study involving five laboratories and a total of six columns. Three chlortetracycline hydrochloride samples were analysed. The main component and the impurities were determined. An analysis of variance, treating each column as a different laboratory, showed an absence of consistent between-laboratory bias and the presence of a significant laboratory-sample interaction. The repeatability and the reproducibility of the method, expressed as relative standard deviations of the result of the determination of chlortetracycline hydrochloride, were calculated to be 0.9% and 1.1% respectively.
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  • 69
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    Chromatographia 37 (1993), S. 627-634 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; ODS phases ; NMR and FTIR characterization ; Stationary phase functionality
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    Topics: Chemistry and Pharmacology
    Notes: Summary Two spectroscopic methods, solid state NMR and diffuse reflectance FTIR, have been used in conjunction with liquid chromatographicretention data to identify and distinguish the functionality of octadecylsilica (ODS) stationary phases. NMR and FTIR spectra are indicative of various features of the different functionalities of the phases and this information can be used to elucidate the configuration of the organosilyl moiety in the ODS on the silica surface and explain why DSS phases have different molecular shape (mainly planarity) recognition capability.
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  • 70
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    Chromatographia 37 (1993), S. 423-428 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Polymer-modified silica ; Polypyrrole cloride ; Polypyrrole dodecylsulfate ; Small molecules ; Polyaromatic hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Polypyrrole chloride and polypyrrole dodecylsulfate coated-silica packing materials have been synthesized. Reverse-phase chromtographuy was employed to characterise both packings. A series of test compounds with known properties was used as molecular probes. They included benzene and derivatives, basic drugs, and polyaromatic hydrocarbons. A commericial C18 column was also used for the purpose of comparison in some cases.
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  • 71
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Arsenic compounds ; Polymeric styrene divinylbenzene phase ; Ion-pairing
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The resolving power of an ion-pair reversed-phase liquid chromatography method, on a polymeric stationary phase (PRP-1) with an alkaline aqueous mobile phase (pH=9) containing tetrabutylammonium cation as ion-pairing agent, is compared with a traditional ion-pairing system using an octadecyl-modified silica column and a neutral aqueous mobile phase (pH=7.3). This chromatographic system (PRP-1 column) provides a rapid means for the determination of two of the most important arsenic species, arsenobetaine and arsenite. Addition of methanol (5%) to the aqueous mobile phase allows the differentation of arsenobetaine from the system peak when using UV detection.
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  • 72
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gravity-flow column chromatography ; Provitamin A determination
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The provitamin A content of some food samples was determined by methods involving MgO: Hyflosupercel gravityflow column chromatography (GFCC) and reversed phase high performance liquid chromatography (HPLC), the quantitation being done by external standardization (HPLC-ES) or internal standardization (HPLC-IS) with Sudan. The results obtained with α- and β-carotene in carrots, β-carotene and β-cryptoxanthin in papaya and β-carotene in tomato and kale agreed well, showing that any of the these techniques can be used, provided the analysis is done under optimum conditions. Good separation of the different provitamins using GFCC depends on the analyst's skill and visual acuity. HPLC-ES required a constant supply of provitamin standards, thus the varying purity of commercially available standards and the high instability of these compounds could pose grave problems. Due to the stability of Sudan, HPLC-IS appeared to be the method of choice although passage of the extract through a MgO: Hyflosupercel minicolumn was required prior to injection to separate chlorophylls, dihydroxy- and polyoxycarotenoids which would otherwise elute with Sudan. Nonconformity of the Sudan structure to those of the provitamins did not effect the quantitative results. The chromatographic separation, identity and quantification of the provitamins could be more easily established by using HPLC-IS, complemented with GFCC.
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  • 73
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    Chromatographia 33 (1992), S. 103-112 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Gas chromatography ; Chiral separations ; Allethrin ; Cypermethrin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Liquid and gas chromatographic separations of the pyrethroid insecticides allethrin and cypermethrin have been investigated with various achiral and chiral stationary phases. Diastercomeric and enantiomeric selectivity was observed for cypermethrin on a Pirkle-type chiral LC stationary phase, but very strong interactions and therefore long retention times prevented the separation of allethrin on this phase. Trans-allethrin isomers were separated on a chiral β-cyclodextrin RP-HPLC column while cypermethrin showed some difficulties on this phase due to isomerization. Diastereomeric but no enantiomeric selectivity by GC was achieved for cypermethrin with an apolar DB 5 capillary. GC separation of the diastereomers was used to study the selective photodegradation of cypermethrin isomers after forestry applications. Chiral β-cyclodextrin-based GC phases showed some enantioselectivity for cis- and trans-allethrin isomers. A separation of the eight isomers into six partially resolved peaks was achieved by GC with a coupled column consisting of chiral permethylated β-cyclodextrin and DB 1701 as stationary phases. This combination was used to characterize allethrin formulations intended for indoor use and to investigate allethrin products formed by ozonolysis of thin films of the insecticide.
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  • 74
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiralcel OD ; N-Alkyl-N-methylanilineN-oxide enantiomers ; Chiral nitrogen centre ; Flavin-containing monooxygenase
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A high-performance liquid chromatographic method for the resolution of the enantiomers of a series ofN-alkyl-N-methylanilineN-oxides is reported. The resolutions were achieved using a Chiralcel, OD chiral stationary-phase with a mobile-phase of hexane and ethanol in varying proportions. The chromatographic order of elution of the enantiomers ofN-ethyl-N-methylanilineN-oxide was determined to be (+)-(R) before (−)-(S).
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  • 75
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    Chromatographia 37 (1993), S. 539-542 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Sotolon ; Vin jaune ; Flor-sherry
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Sotolon (4,5-dimethyl-3-hydroxy-2(5H)-furanone) is a key flavour compound in the french flor-sherry “Vin jaune”. This compound was determined quantitatively by extraction of 25 ml of wine on a XAD-4 resin, elution with diethyl ether, separation by HPLC on a Lichrospher 100 Diol column, elution with dichloromethane/hexane (60/40) and UV detection at 232 nm. The amount of sotolon in “Vin jaune” (120 to 268 μg/l) was related to the development of the yeast film over a period of 6 years. Only 6 to 51 μg/l were found in the “Vin de paille” which is made with overmaturated grapes of the same Savagnin vine-plant but without development of yeasts, and 80 to 140 μg/l in “Tokai” which are partly grown under a yeast film.
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  • 76
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Column-switching ; Determination of triamterene ; Fluorescence detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A liquid chromatographic method incorporating column-switching and fluorimetric detection for the determination of triamterene in untreated urine, is described. The urine samples (5 μL) were directly introduced onto an Hypersil ODS-C18, 30 μm (20 mm×2.1 mm I.D.) pre-column. Polar urinary compounds were removed by flushing the pre-column with water for 1 min, and the analyte was then switched onto an HP-LiChrospher RP C18,5 μm (125 mm×4mm ID) analytical column using an acetonitrile/phosphate buffer gradient elution. Fluorescence detection was performed at 230 nm excitation and 430 nm emission wavelengths. The recovery of drug was 102±2% in the 0.10–20.0 μg/mL concentration range, the limit of detection being 5 ng/mL. A validation of the usefulness of this procedure was accomplished by analysing urine extracts obtained from real samples.
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  • 77
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Characterization of reversed phases ; Column hydrophobicity ; Column hydrophylicity
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    Topics: Chemistry and Pharmacology
    Notes: Summary The validity of a method for characterizing stationary phases for reversed-phase, liquid chromatography, based on the use of homologous series, has been evaluated. The method is based on a retention model which describes the dependence of the logarithm of the capacity factor on mobile phase composition and the carbon number of specific homologous series. A first-order as well as a second-order version of this model was investigated. The second-order model proved to be a significant improvement on the first-order model, even for smaller mobile-phase ranges. Nevertheless both models showed a significant lack of fit, reflecting the incompleteness of these models. Therefore, it is very questionable whether this method is suitable to describe HPLC-column characteristics like hydrophobicity and hydrophylicity.
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  • 78
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Copoly(styrene/acrylonitrile) ; Gradient elution ; Precipitation chromatography of polymers ; Solubility of polymers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Copolymers from styrene and acrylonitrile could be separated according to composition by gradient elution through methanol after injection inton-heptane and sudden addition of 50, 60, or 70 vol% tetrahydrofuran. The peak sequence was the same as with a common binary gradientn-heptane/tetrahydrofuran, i.e., retention increased with acrylonitrile content of the samples. With copolymers containing 37, 31, or 26% acrylonitrile, the elution characteristics in the ternary systems could be logically extrapolated towards the points measured in the corresponding binary gradient system.
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  • 79
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral recognition ; Aminoalkylphosphonic acid derivatives ; β-cyclodextrin bonded phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An acetylated β-cyclodextrin column was used to analyse the enantiomeric resolution of a number of aminophosphonic acids. Effects of the structure of these compounds on the extent of separation was examined. Molecular modelling studies were also carried out in an attempt to relate any interaction between the amino and phosphonic acid groups to chiral recognition by the stationary phase.
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  • 80
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    Chromatographia 33 (1992), S. 177-185 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Diuretics ; Screening and determination of diuretics
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary This critical review of different methods proposed for the determination and screening of diuretics is directed mainly, because of its potential application, towards highperformance liquid chromatography.
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  • 81
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    Chromatographia 33 (1992), S. 218-224 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Peak ; Pattern recognition ; Prediction interval
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary It is still difficult to determine peaks and peak boundaries properly, though peak recognition is very important for the precision of quantitative data. A new computer program overcomes these problems using a method which is adapted from human judgements. The algorithm was developed for HPLC but can also be used in other fields of analytical chemistry.
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  • 82
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral separation ; Association constants ; Frontal analysis ; Cyclodextrin bonded-phases
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The interaction between cyclodextrin and the drug (1R,2S,3S,4S)-(5Z)-7-(3-((phenylsulfonyl)amino)bicyclo[2.2.1]hept-2-yl)hept-5-enoic acid ((+)-S-145), was studied using α-, β-, and γ-cyclodextrin bonded-phase columns. Retention behavior of (+)-S-145 on these columns revealed that the strength of inclusion was β→γ→α-cyclodextrin. Interaction between β-cyclodextrin and (+)-S-145 was found to increase as the proportion of carboxylic ion in the (+)-S-145 molecule increased. Comparison of binding capacities of these bondedsilica gels obtained by frontal analysis and surface coverage indicated that availability of the immobilized β- and γ-cyclodextrin was 20–25%. The synthesized β-cyclodextrin bonded-phase column was superior to that of commercial columns in terms of chiral separation of (±)-S-145. A typical usage of the β-cyclodextrin column is discussed for separation of (±)-S-145 in plasma samples.
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  • 83
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Primary and secondary aliphatic alcohols ; Aqueous derivatization ; Phthalic acid monoesters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Determination of primary and secondary aliphatic alcohols in aqueous and nonaqueous solutions by high-performance liquid chromatography (HPLC) is described. The alcohol is derivatized with phthalic anhydride to yield the corresponding monophthalate. Separation of the derivative is achieved on an ODS-10 reverse phase (RP) column by elution with an appropriate isocratic mobile phase of acetonitrile and aqueous phosphoric acid (0.1%). Detection is accomplished by UV absorption at 230 nm or 280 nm giving linear calibration plots, for alcohols in aqueous solution from 0.05% to 0.50% (w/v) and in pyridine solution from 0.0025% to 0.0250% (w/v).
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  • 84
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Hybrid mobile phases containing alcohols ; Solute-micelle association constants ; Polynuclear aromatic hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The interaction between some polynuclear aromatic hydrocarbons of environmental concern, and sodium dodecylsulphate and hexadecyltrimethylammonium bromide in the presence of methanol, 2-propanol and n-butanol has been evaluated by high-performance liquid chromatography using micellar mobile phases. Solute-micelle association constants have been determined for the compounds investigated. The results show that the addition of the alcohol to the mobile phase decreases the association constant values, methanol 〈2-propanol 〈n-butanol, relative to those in the absence of any additive.
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  • 85
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    Chromatographia 38 (1994), S. 571-578 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Wine ; Biogenic amines ; Solid-phase extraction ; Derivatization
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A method suitable for the determination of 19 biogenic amines in wine has been developed. The method involves derivatization of amines by treatment with dansyl chloride and solid-phase extraction of the derivatives. Prior to the derivatization procedure, clean-up of the wine sample with polyvinylpyrrolidone is carried out. Reversed-phase gradient elution HPLC with UV detection at 250 nm was used to determine these compounds. Some consideration was given to the effect of temperature on the separation process. Linearity of derivatization was obtained for amounts of all the biogenic amines ranging from 500 μg·L−1 to 20 mg·L−1. Limits of detection (signal-to-noise ratio=3) of the amines were similar for all the dansylderivatives (between 50 and 150 μg·L−1). Addition of standard amines was used for the determination of amine recoveries. These were better than 85% for ethanolamine, tryptamine, phenetylamine, putrescine, cadaverine and histamine. The overall process was succesfully applied to identify and quantify biogenic amines in white and red wines.
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  • 86
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Chiral/enantiomeric iseparation ; Cellulose-based chiral phases ; Tifluadom analogues ; 2-acylaminomethyl-1,4-benzodiazepines
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The resolution of nine recamic mixtures of tifluadom analogues has been evaluated using the chiral stationary phases Chiralcel OD and Chiralcel OJ. The separation was performed on an analytical scale to optimize the conditions for chiral resolution, approaching baseline separation, of the two enantiomers. Eight racemates were baseline separated on Chiralcel OJ using a mobile phase of hexane/2-propanol.
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  • 87
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Diol silica gels ; Carbohydrates ; Evaporative light scattering detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Bonded silica columns have been evaluated for their ability to separate carbohydrates and polyols. Mobile phases consisting of dichloromethane/methanol produced the best separations in comparison with the acetonitrile/water mixtures commonly used with amino columns. Of all the bonded phases tested, LiChrospher Diol silica provided the best separations, and selectivities were not very different from those obtained on the most popular system using an amino bonded phase and acetonitrile/water as eluent. In addition, diol columns with a dichloromethane/methanol eluent offer excellent stability with no Schiff’s base formation of reducing sugars. Using an evaporative light scattering detector, low limit detection is obtainable (20 ng of glucose from a column) and gradient elution is quite feasible.
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  • 88
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Phenolic compounds ; Ion-pair solid-phase extraction ; Comparison of sorbents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A comparative study of the solid phase extraction of phenolic compounds in water was carried out. Three different sorbents, C18, CH and PLRP-S, were tested for the preconcentration process in order to determine phenolic compounds in water at μg l−1 levels by reversed-phase LC separation and diode-array detection. The addition of an ion-pair reagent in the extraction process was also studied in order to increase the breakthrough volume of some compounds. Using the optimized conditions the limit of detection was less than 0.5 μg l−1, the maximum admissible concentration (MAC) in drinking water. The method was applied to determine phenolic compounds in Ebro river water however no phenols were found within the detection limits of the method.
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  • 89
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Extraction-determination ; Basic drugs ; Blood
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new method for the extraction of basic drugs from whole blood based on the use of a buffered protein precipitating reagent at pH9, to form NiWO4 in biological fluids and a ternary organic extracting phase of density below 1 is proposed. The extract is analysed by high performance liquid chromatography using a Hypersil C8 column and detection at 230 nm; the mobile phases used consist of binary mixtures of acetonitrile and aqueous solutions containing 20 mmol/l ofn-propylamine at pH 5 andn-hexylamine at pH 4, as blockers of the free silanol groups. The proposed method was applied to the determination of 16 basic drugs including narcotics, analgesics, cocaine-related compounds and adulterants, as well as 8 benzodiazepines, in whole blood.
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  • 90
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    Chromatographia 39 (1994), S. 62-66 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Column switching ; Imidazolinone herbicides in soil ; Imazethapyr ; Imazapyr
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A column-switching method using two separation columns combined with UV detection at 260 or 236 nm has been used to determine the imidazolinone herbicides imazethapyr and imazapyr in soils. The residues were extracted from the soil with 0.1 M aqueous sodium carbonate solution and, after adjusting the pH to 2.0, the solution was partitioned with dichloromethane. Limits of determination for imazethapyr and imazapyr were 3 μg/kg. Recoveries were from 55 to 75% for both imidazolinone herbicides in the range 3–100 μg/kg in soil.
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  • 91
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous graphitized carbon ; Ring-substituted aniline derivatives ; Electronic interactions ; Principal component analysis
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The retention characteristics of 22 aniline derivatives were determined on a porous, graphitized-carbon column in unbuffered acetonitrile-water and methanol-water mixtures. Each aniline derivative gave symmetrical peaks in each eluent without buffers. Good linear correlations were found between the log k′ and the concentration of the organic component in the eluent. The slope and intercept values differed according to the type of organic modifier and the charcter, number and position of substituents, indicating the different selectivities of methanol and acetonitrile and the good separating power of the column. Multivariate mathematical-statistical calculations proved that the retention of ring-substituted aniline derivatives is mainly governed by electronic parameters and the hydrogen acceptor capacity of substituents.
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  • 92
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion-pairing ; Furosine ; Pyridosine ; Milk
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An ion-pair, reversed-phase, liquid chromatographic procedure using UV detection for quantitation of furosine is described. The standard plot was linear (r〉0.999) over a 5 ng range. An authentic synthesised sample of furosine was used for calibration. Commerical milk samples were analyzed by the described procedure.
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  • 93
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Automated peak detection ; Discrete Fourier transform ; Frequency acquisition and filtering ; Peak detection
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The principle of automated chromatographic peak detection and analysis software is summarized, and critical steps are systematically studied. As the only parameter to be entered is the acquisition frequency, evaluation of its effect on software performance is discussed. In the case of relatively noisy chromatograms, it is shown experimentally that numerous points per peak have to be taken, leading to quite fast computer acquisition procedures. The use of discrete Fourier transform filtration techniques can modify peak shapes and a comparative study evaluates the relative errors induced in the shapes and characteristics of the chromatographic profiles. Optimisation of filtering conditions is achieved and it is shown that for a filter position only 2% of the Nyquist frequency no deformation occurs in the chromatographic profile. Detection of the start and finish of chromatographic peaks is optimized according to a simple four step iterative procedure. In the case of simulations, the difference between the values used to simulate peaks and those calculated by the software are less than 1%.
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  • 94
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    Chromatographia 39 (1994), S. 246-248 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Mercury ; Diphenylethynylmercury
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A new procedure for derivatisation of inorganic mercury(II) to diphenylethynylmercury with simultaneous extraction into dichloromethane is proposed. The organomercury derivative is effectively analysed by HPLC using UV detection. The calibration curve is linear over three orders of magnitude (0.02–50 mg L−1 Hg); the detection limit is 0.1 ng Hg. A preliminary study of the effect of potential interfering agents, in particular Cu(II), Zn(II), Cd(II), Pb(II), and cysteine, and applications of the present methodology to real environmental samples are presented.
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  • 95
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Fluoropyrimidine drugs ; Pharmacokinetics of doxifluridine ; Chemotherapy
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A reversed phase high performance liquid chromatographic method has been developed for the simultaneous determination of the pro-drug 5′-deoxy-5-fluorouridine (5′-dFUR), its metabolite 5-fluorouracil (5-FU) and some fluorinated pyrimidines involved in the metabolic activation process of 5-FU. The method has been used to monitor the bioavailability of 5′-dFUR and 5-FU in patients undergoing anticancer chemotherapy. Serum sample treatment involves addition of internal standard (5-bromouracil), protein precipitation with saturated ammonium sulphate solution and liquid-liquid extraction with ethyl acetate-isopropanol (90 ∶ 10 v/v). Urine is simply diluted with mobile phase and injected. The average recovery from serum (at 0.5 μg/mL level) was 95.0%±1.4 for 5′-dFUR and 86.3%±3.5 for 5-FU. A linear response extending over four decades of concentration was observed. Detection limits in the low ng/ mL range were obtained using a 250 μL sample size and a 20 μL injection volume. Within-day and between-day coefficients of variation were below 4 and 10%, respectively.
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  • 96
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Flow injection analysis ; Combined flow injection/HPLC ; Carbamate pesticides
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary An integrated flow injection (FI)/HPLC system for the total and individual determination of carbamate pesticides (propoxur, carbofuran and carbaryl) is proposed. The determination is based on the alkaline hydrolysis of the analytes and subsequent coupling with diazotized sulphanilic acid to yield the monitored dyes with or without a prior separation step by HPLC in a C18 column. The calibration curves obtained are linear in the μg/ml range and r.s.d. values are between 0.5 and 3.7% in all instances. Injection of the sample into the FI manifold allows the total pesticide content in the sample to be screened. The manifold thus acts as a post-column reactor/detector of the chromatograph for samples with high overall carbamate content, which are also injected into the HPLC instrument. The performance was checked with contaminated water samples.
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  • 97
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; α1 glycoprotein ; Enantioseparation ; β-blocking agents
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The enantioselectivity of the α1 glycoprotein chiral stationary phase, Chiral AGP® has been evaluated for a number of β-blocking agents. A correlation has been found between the retention behaviour on this stationary phase and the hydrophobicity of the compounds. The separation factor α is higher for compounds that are well retained. Retention, and thus α, are also controlled by pH and the percentage of organic modifier in the mobile phase.
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  • 98
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Perfluoroalkylated polymer-gel packings ; Aromatic and fluorine-containing compounds
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Porous, perfluoroalkylated polymer-gels for column packings in high-performance liquid chromatography (HPLC) were prepared by suspension polymerization of heptadecafluorodecyl arcylate and ethylene glycol dimethacrylate. The packings showed no abnormal retention for ionic or aromatic compounds, due to the lack of ionic or aromatic groups. In addition, the packings showed no excessive retention for strongly hydrophobic compounds which is often the case with long-chain, alkylated silica gels and polymer gels. This is due to the extremely low surface energy of perfluoroalkyl groups. Therefore, perfluoroalkylated polymer gels enable isocratic HPLC separation of solutes with significantly different hydrophobicity.
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  • 99
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous glass ; Surface free energy ; Film pressure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
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  • 100
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    Chromatographia 33 (1992), S. 478-484 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Porous glass adsorbents ; Surface free energy ; Oriented adsorption of hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The relationship between the specific capacity factor (k/S, where k is the capacity and S is the surface area of the sorbent, in m2) in the liquid chromatography of aromatic hydrocarbons and the adsorption energy (-°GA) has been investigated. The previously published results, based on the calculation of the work of adhesion (WSA) from contact angles, were re-examined and a new hypothesis on interactions at interfaces was employed. Direct proportionality has been found between k/S and-°GA, which allows prediction of the chromatographic behavior of adsorbates on sorbents. The surface free energy components were calculated in order to determine-°GA in terms of the work of adhesion. The dispersion component of the surface free energy of glass was obtained from the adsorption isotherm of n-octane and it was found that the hydrocarbon molecules are adsorbed in an oriented position. The contact angles of liquids on the outer surface of porous solids do not yield reliable values of WSA and of the surface free energy components. A higher intermolecular attraction increases WSA and decreases the contact angle in pores.
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