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  • Artikel  (58)
  • Artikel: DFG Deutsche Nationallizenzen  (58)
  • Chemical Engineering
  • Electronic structure and strongly correlated systems
  • Saccharomyces cerevisiae
  • kinetics
  • Springer  (58)
  • 1985-1989  (58)
  • Chemie und Pharmazie  (58)
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  • Artikel: DFG Deutsche Nationallizenzen  (58)
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  • 1
    ISSN: 1572-8773
    Schlagwort(e): Manganese ; Electron spin resonance ; Superoxide dismutase ; Saccharomyces cerevisiae ; Yeast
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary Manganese accumulation was studied by room-temperature electron spin resonance (ESR) spectroscopy inSaccharomyces cerevisiae grown in the presence of increasing amounts of MnSO4. Mn2+ retention was nearly linear in intact cells for fractions related to both low-molecular-mass and macromolecular complexes (‘free’ and ‘bound’ Mn2+, respectively). A deviation from linearity was observed in cell extracts between the control value and 0.1 mM Mn2+, indicating more efficient accumulation at low Mn2+ concentrations. The difference in slopes between the two straight lines describing Mn2+ retention at concentrations lower and higher than 0.1 mM, respectively, was quite large for the free Mn2+ fraction. Furthermore it was unaffected by subsequent dialyses of the extracts, showing stable retention in the form of low-molecular-mass complexes. In contrast, the slope of the line describing retention of ‘bound’ Mn2+ at concentrations higher than 0.1 mM became less steep after subsequent dialyses of the cell extracts. This result indicates that the macromolecule-bound Mn2+ was essentially associated with particulate structures. In contrast to Cu2+, Mn2+ had no effect on the major enzyme activities involved in oxygen metabolism except for a slight increase of cyanide-resistant Mn-superoxide dismutase activity, due to dialyzable Mn2+ complexes.
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 86 (1989), S. 65-70 
    ISSN: 1573-4919
    Schlagwort(e): Hex A ; Hex B ; N-acetyl-glucosaminidases ; kinetics ; thermodynamic transitions ; ion-exchangers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Summary The kinetic and thermodynamic properties of N-acetyl-β-D-glucosaminidase A (Hex A) and N-acetyl-β-D-D-glucosaminidase β (Hex B) from goat testes were investigated in free and bound (after binding them on ion-exchangers such as DEAE- or CM-cellulose respectively) forms. The optimum pH of free Hex A and Hex B was at 4.2 and 5.4, whereas the bound forms showed the optimum pH at 4.0 and 5.2 respectively. While apparent Km of free and bound Hex A (0.8 and 1.0 mM respectively) did not differ, the Km of Hex B increased when bound on CM-cellulose (Km of free Hex B = 0.96 mM versus bound Hex B = 1.6 mM). Though the free Hex A was more thermo-labile than the free Hex B, both isozymes, on insoluble matrices decayed at faster rates on heating. Activation analysis revealed that the energy of activation (E infa supo ) for transition state of free Hex B (81 Kcal deg−1 mole−1) did not differ from E infa supo of bound Hex B. On the other hand, E infa supo of free Hex A declined from 77.2 to 71.1 Kcal deg−1 mole−1 when heat transitions were carried out in free and bound state respectively. Thermodynamic analysis suggested a change in entropy of activation (ΔS*) of free Hex A and Hex B as 200 and 211 eu respectively. While ΔS* of Hex B did not change after heat transitions, ΔS* of Hex A was 182.5 eu.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 86 (1989), S. 171-179 
    ISSN: 1573-4919
    Schlagwort(e): porcine glucokinase ; purification ; kinetics ; sulfhydryl-related states
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract Porcine hepatic glucokinase (ATP: D-hexose 6-phosphotransferase EC 2.7.1.1) has been purified by a modification of the procedure for its purification from rats. However, difficulties were encountered with endogenous proteases and the reliability of a source for porcine livers. The molecular weight has been determined to be 60 400 ± 1400 by sodium dodecyl sulfate, polyacrylamide gel electrophoresis. The enzyme has been characterized kinetically. The parameter values, S 0.5 (glucose) and Hill coefficient (nH) are 2.4 mM and 1.9 respectively under sulfhydryl-reducing conditions. The enzyme undergoes the two sulfhydryl-related decays of its activity previously observed in the enzyme isolated from rat (Tippett PS, Neet KE: Arch Biochem Biophys 222:285–298, 1983). The enzyme is inhibited by palmitoyl-CoA, K i (apparent) = 1.0 µM, nH = 1.8; this concentration of inhibitor is significantly below its critical micelle concentration. Physically and kinetically glucokinase isolated from pig is similar to the enzyme isolated from rat. The porcine system provides a second source for isolation and further characterization of this important and unusual enzyme.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    The protein journal 8 (1989), S. 529-548 
    ISSN: 1573-4943
    Schlagwort(e): carmin ; association-dissociation ; denaturation ; reaggregation ; kinetics ; reversibility ; hydrophobic interaction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The effect of a decrease inpH on the structural integrity of carmin has been monitored by a variety of biophysical techniques. The protein undergoes initial dissociation up topH 3.5–4.0 without any significant denaturation. Below thispH the process of dissociation and denaturation appears to be simultaneous. Further, in thepH range of 2.5–1.6 the protein reassociates to probably a different polymer resulting from possibly, an entropically driven hydrophobic interaction. The process of dissociation appears to be reversible to a large extent. The process of denaturation appears to be governed by the kinetic path that the denatured protein molecule follows either by a sudden decrease inpH or through a gradual decrease inpH. These results are interpreted while keeping in view the oligomeric and globular structure of carmin at neutralpH. The results would help in understanding of structure-function relationship of the protein and its role in hydrogen ion bindingin vivo.
    Materialart: Digitale Medien
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  • 5
    ISSN: 1432-1424
    Schlagwort(e): sodium ; pyruvate ; transport ; proximal tubule ; kinetics ; kidney
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary The experiments reported in this paper aim at characterizing the carboxylic acid transport, the interactions of pyruvate and citrate with their transport sites and specificity. The study of these carriers was performed using isotopic solutes for the influx measurements in brush-border membrane vesicles under zerotrans conditions where the membrane potential was abolished with KCl preloading with valinomycin or equilibrium exchange conditions and Δψ=0. Under zerotrans condition and Δψ=0, the influence of pyruvate concentrations on its initial rates of transport revealed the existence of two families of pyruvate transport sites, one with a high affinity for pyruvate (K t =88 μm) and a low affinity for sodium (K t =57.7mm) (site I), the second one with a low affinity for pyruvate (K t =6.1mm) and a high affinity for sodium (K t =23.9mm) (site II). The coupling factor [Na]/[pyruvate] stoichiometry were determined at 0.25mm and 8mm pyruvate and estimated at 1.8 for site I, and 3 when the first and the second sites transport simultaneously. Under chemical equilibrium (Δψ≅0) single isotopic labeling, transport kinetics of pyruvate carrier systems have shown a double interaction of pyruvate with the transporter; the sodium/pyruvate stoichiometry also expressed according to a Hill plot representation wasn=1.7. The direct method of measuring Na+/pyruvate stoichiometry from double labeling kinetics and isotopic exchange, for a time course, gives an=1.67. Studies of transport specificity, indicate that the absence of inhibition of lactate transport by citrate and the existence of competitive inhibition of lactate and citrate transports by pyruvate leads to the conclusion that the low pyruvate affinity site can be attributed to the citrate carrier (tricarboxylate) and the high pyruvate affinity site to the lactate carrier (monocarboxylate).
    Materialart: Digitale Medien
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  • 6
    Digitale Medien
    Digitale Medien
    Springer
    The journal of membrane biology 108 (1989), S. 253-261 
    ISSN: 1432-1424
    Schlagwort(e): Chara ; Cl− ; cotransport ; reaction kinetic model ; pH ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary H+-coupled transport in plant and fungal cells is relatively insensitive to external pH (pH o ). H+-coupled Cl− transport at the plasma membrane ofChara corallina was studied to explore the phenomena responsible for this insensitivity. Raising pH o from a control value of 7.5 to 9.0 results in a modest (2.5-fold) decline inJ max and increase inK m . Further increase in pH o results in a selective increase inJ max, in accordance with predictions from a reaction kinetic model of the transport system (Sanders, D., Hansen, U.-P., 1981.J. Membrane Biol. 58:139–153). Increase in cytosolic Cl− concentration ([Cl−] c ) also results in a selective decrease inJ max at pH o =7.5. Quantitative kinetic modeling of the results is not possible if it is assumed that the sole effect of pH o isvia mass action on the binding of external H+ to a transport site. If, instead, the dependence of cytosolic pH (pH c ) on pH o (Smith, F.A., 1984,J. Exp. Bot. 35:1525–1536) is taken into account along with the dependence of Cl− influx on pH c (Sanders, D., 1980,J. Membrane Biol. 53:129–141), then the observed modest changes in Michaelis parameters can be accommodated by a reaction kinetic model. The quantitative parameters of the model yield respective pK a s of the internal and external H+-binding sites=7.85 and 7.2, respective dissociation constants of the internal and external Cl−-binding sites=160 and 40 μm, and an additional, kinetically transparent, H+-binding site with a pK a 〉8.0. The quantitative model independently predicts the response ofJ max andK m to acidic conditions. The results are discussed in terms of the general physiological requirement that fluxes through H+-coupled transport systems are relatively insensitive to environmental variation in pH o . It is proposed that (i) the weak (but finite) dependence of pH c on pH o , coupled with (ii) the strong dependence of H+-coupled transport on pH c are instrumental in endowing H+-coupled transport systems with a relative insensitivity to variation in pH o . This hypothesis might also explain why pH c in plants and fungi is not acutely controlled with respect to variation of pH o .
    Materialart: Digitale Medien
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    The journal of membrane biology 110 (1989), S. 57-65 
    ISSN: 1432-1424
    Schlagwort(e): fluorescence ; water transport ; vasopressin ; kidney collecting tubule ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary Water transport across the mammalian collecting tubule is regulated by vasopressin-dependent water channel insertion into and retrieval from the cell apical membrane. The time course of osmotic water permeability (P f ) following addition and removal of vasopressin (VP) and 8-Br-cAMP was measured continuously by quantitative fluorescence microscopy using an impermeant fluorophore perfused in the lumen. Cortical collecting tubules were subjected to a 120 mOsm bath-to-lumen osmotic gradient at 37°C with 10–15 nl/min lumen perfusion and 10–20 ml/min bath exchange rate. With addition of VP (250 μU/ml), there was a 23±3 sec (sem,n=16) lag in whichP f did not change, followed by a rise inP f (initial rate 1.4±0.2×10−4 cm/sec2) to a maximum of 265±10×10−4 cm/sec. With addition of 8-Br-cAMP (0.01–1mm) there was an 11±2 sec lag. For [8-Br-cAMP]=0.01, 0.1 and 1mm, the initial rate ofP f increase following the lag was (units 10−4 cm/sec2): 1.1±0.1, 1.2±0.1 and 1.7±0.3. MaximumP f was (units 10−4 cm/sec): 64±4, 199±9 and 285±11. With removal of VP,P f decreased to baseline (12×10−4 cm/sec) with aT 1/2 of 18 min; removal of 0.1 and 1mm 8-Br-cAMP gaveT 1/2 of 4 and 8.5 min. These results demonstrate (i) a brief lag in theP f response, longer for stimulation by VP than by 8-Br-cAMP, representing the transient build-up of biochemical intermediates proximal to the water channel insertion step, (ii) similar initialdP f /dt (water channel insertion) over a wide range of [8-Br-cAMP] and steady-stateP f values, and (iii) more rapidP f decrease with removal of 8-Br-cAMP than with VP. These pre-steady-state results define the detailed kinetics of the turn-on and turn-off of tubuleP f and provide kinetic evidence that the rate-limiting step for turn-on ofP f is not the step at which VP regulates steady-stateP f . If water channel insertion is assumed to be the rate-limiting step in the turn-on ofP f , these results raise the possibility that water channels must be activated following insertion into the apical membrane.
    Materialart: Digitale Medien
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  • 8
    ISSN: 1432-1424
    Schlagwort(e): charybdotoxin ; erythrocytes ; iodination ; kinetics ; peptides ; potassium channels ; scorpions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary Two charybdotoxin peptides were purified from venom of the Israeli scorpion,Leiurus quinquestriatus hebraeus. Microsequencing of the most abundant toxin, ChTX-Lq1, revealed identity with the 37-residue peptide previously sequenced by Gimenez-Gallego et al. [Gimenez-Gallego, G., et al.,Proc. Natl. Acad. Sci. USA 85:3329–3333 (1988)]. Sequence data on the minor peptide, ChTX-Lq2, showed substantial homology to ChTX-Lq1 with differences observed at eight positions. These two charybdotoxin sequences, along with that of noxiustoxin, define a distinct family of scorpion peptide toxins with activity against K+ channels. Both charybdotoxin homologs inhibited Ca2+-dependent K+ efflux from human erythrocytes with similar potency,K 0.5∼-40nm. In planar bilayer assays of single K(Ca) channels from rat muscle, ChTX-Lq1 and ChTX-Lq2 blocked with intrinsicK d's of 1.3 and 43nm, respectively, in the presence of 50mm external KCl. A new application of dwell-time histogram analysis of single-channel blocking events was used to characterize the kinetic homogeneity of toxin samples and the blocking kinetics of ChTX derivatives. The lower blocking affinity of ChTX-Lq2 was the combined result of a faster dissociation rate and a slower association rate as compared to ChTX-Lq1. The blocking activity of two mono-iodinated derivatives of ChTX-Lq1 was also analyzed. Blocked dwell-time histograms of the iodinated peptides were characterized by predominately brief (0.2–2 sec) blocking events in comparison to the native toxin (20 sec). Histogram analysis revealed that mono-iodination of ChTX-Lq1 impairs blocking activity by adverse effects on both dissociation and association rate constants. Frequency density histograms of single channel blocking events provide a sensitive assay of toxin purity suitable for quantitating structure-activity relationships of charybdotoxin derivatives.
    Materialart: Digitale Medien
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Investigational new drugs 7 (1989), S. 27-36 
    ISSN: 1573-0646
    Schlagwort(e): kinetics ; fluorouracil ; bolics ; administration
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Thymidylate synthase (TS) is the enzyme target of 5-fluorouracil (FUra) that recent laboratory and clinical studies with folinic acid (calcium leucovorin) suggest may mediate important antitumor cytotoxicity. Measurement in carcinoma tissue of parameters related to TS inhibition by 5-fluorodeoxyuridylate (FdUMP), by analogy to hormone receptor analysis, should be useful to determine which patients should receive fluoropyrimidine drug therapy and to evaluate folinic acid requirements. Folinic acid is metabolized to 5,10-methylenetetrahydropteroylglutamine (CH2FH4), which must be present in large excess to effect desired levels of maximal inhibition of TS, by promoting formation and stabilization of TS-FdUMP-CH2FH4 ternary complexes. In patients with metastatic disease, serial biopsies of tumor and normal tissues for studies of pharmacodynamic responses to test-dose FUra or folinic acid are shown to be easily added to routine intraoperative management. A suitable methodologic approach is described and examples given of assays of free TS, FdUMP, dUMP, and CH2FH4 levels after FUra or folinic acid, that may be useful in future studies aimed at improving the cost-effectiveness of FUra-folinic acid combinations.
    Materialart: Digitale Medien
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Investigational new drugs 7 (1989), S. 155-161 
    ISSN: 1573-0646
    Schlagwort(e): heterogeneity ; polyamines ; cell killing ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Abstract The effects of α-difluoromethylornithine (DFMO) on survival, cell kinetics and polyamine levels were studied on two clones of human astrocytoma in vitro. The survival responses were dose and time dependent; and treatments with DFMO which lasted for 72 h resulted in heterogeneous responses with one clone being up to 6 times more sensitive than the other. Shorter treatments produced more uniform killing in the clones. A continuous exposure of the cells to 5 mM DFMO resulted in a rapid decrease in putrescine values in both clones, followed by decreases in the spermidine levels. These effects were closely followed by 148% to 170% increases in cell population doubling times, and a lowering of saturation densities. No clear correlations could be established among baseline polyamine levels and cell kinetics or survival responses to DFMO treatments.
    Materialart: Digitale Medien
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Journal of pharmacokinetics and pharmacodynamics 17 (1989), S. 47-66 
    ISSN: 1573-8744
    Schlagwort(e): theophyliine ; population analysis ; methylxanthines ; neonatal apnea ; kinetics ; NONMEM
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The population pharmacokinetics of theophylline were evaluated using 391 theophylline serum concentration measurements from 108 neonates and young infants (postnatal age 0–26 weeks), who received theophylline for the treatment of neonatal apnea. A one-compartment pharmacokinetic model with first-order elimination was used, with intravenous aminophylline and oral theophylline administration modeled as zero-order infusions. The effect of a variety of developmental and demographic factors on clearance (CL) and volume (V) were investigated. Hypothesis testing to evaluate potentially significant factors produced a final model in which clearance was based on weight (kg) raised to an exponential power and postnatal age (weeks), with CL (ml/hr)=17.5 (weight)1.28 + 1.17 (postnatal age). Clearance was reduced by 12% for patients receiving parenteral nutrition. Volume of distribution in this population was adequately described using only weight, with V (L)=0.858 L/kg. Bioavailability of orally administered drug was not significantly less than unity. Interindividual variability in clearance was modest, with a coefficient of variation for clearance of 16%. An estimate of interindividual variability in volume could not be obtained. As a measure of residual variability in theophylline serum concentrations, the coefficients of variation for theophylline serum concentrations of 5.0, 10.0, and 13.0 mg/L were found to be approximately, 25, 12, and 9%, respectively. The identification of influential patient factors and the quantification of their influence on theophylline disposition allow for a priori estimates of theophylline pharmacokinetic parameters in these patients.
    Materialart: Digitale Medien
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 267 (1989), S. 179-183 
    ISSN: 1435-1536
    Schlagwort(e): Gel ; swelling ; kinetics ; diffusion
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Tanaka and Fillmore treated the swelling of a gel as a process where a crosslinked polymer network having been initially under uniform stress is expanded by osmotic pressure, sucking up the surrounding fluid medium. We point out that their physical reasoning is unnatural and leads to an unacceptable conclusion; we propose a more sound approach to the same problem. Our treatment assumes that the gel network is extended not by the osmotic pressure of the gel, but rather by the swelling pressure which is generated by the excess fluid penetrating in against the real nature of a polymer network that tends to shrink. The diffusion equation of the fluid, hence, plays a dominant role and gives the distribution of fluid concentration in contrast to Tanaka-Fillmore's scheme. The expression for the distribution of local strain in a spherical gel is deduced from the relation of mechanical balance between two forces, the one is due to the elasticity of the network and the other due to the gradient in the chemical potential of the fluid. The results obtained have forms analytically similar to Tanaka-Fillmore's, but are differ in the physical meanings.
    Materialart: Digitale Medien
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 267 (1989), S. 460-464 
    ISSN: 1435-1536
    Schlagwort(e): Diffusion ; silica gel ; kinetics ; surface area ; proton
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The effect of preparation pH of silica hydrogel on the effective diffusion coefficient of protons in silica hydrogel (D e , m2/s), on surface area of silica gel (S, m2/s) and on particle size of silica gel (D p , mm) was studied. Silica hydrosols were obtained by adding water glass to sulfuric acid. The effective diffusion coefficient of proton in silica hydrogel was determined by the method of diffusion from silica hydrogel plane sheet to a stirred solution of a limited volume. A numerical solution was obtained for the diffusion equation using the Regula Falsi method. Regression analyses of experimental data were conducted. Diffusion of protons in silica hydrogel is a complicated process due to a decelerating effect of the porous structure of silica hydrogel and to the accelerating effects of slow ions such as Na+ and surface diffusion. The effective diffusion coefficient increased with surface area of silica gel, indicating the diffusion of protons on the surface of the silica particles.
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 21 (1989), S. 589-603 
    ISSN: 1573-6881
    Schlagwort(e): Vacuolar membrane H+ATPase ; vacuoles ; Saccharomyces cerevisiae ; catalytic cooperativity of ATP hydrolysis ; VMA genes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Our current work on a vacuolar membrane proton ATPase in the yeastSaccharomyces cerevisiae has revealed that it is a third type of H+-translocating ATPase in the organism. A three-subunit ATPase, which has been purified to near homogeneity from vacuolar membrane vesicles, shares with the native, membrane-bound enzyme common enzymological properties of substrate specificities and inhibitor sensitivities and are clearly distinct from two established types of proton ATPase, the mitochondrial F0F1-type ATP synthase and the plasma membrane E1E2-type H+-ATPase. The vacuolar membrane H+-ATPase is composed of three major subunits, subunita (M r =67 kDa),b (57kDa), andc (20 kDa). Subunita is the catalytic site and subunitc functions as a channel for proton translocation in the enzyme complex. The function of subunitb has not yet been identified. The functional molecular masses of the H+-ATPase under two kinetic conditions have been determined to be 0.9–1.1×105 daltons for single-cycle hydrolysis of ATP and 4.1–5.3×105 daltons for multicycle hydrolysis of ATP, respectively.N,N′-Dicyclohexylcarbodiimide does not inhibit the former reaction but strongly inhibits the latter reaction. The kinetics of single-cycle hydrolysis of ATP indicates the formation of an enzyme-ATP complex and subsequent hydrolysis of the bound ATP to ADP and Pi at a 7-chloro-4-nitrobenzo-2-oxa-1,3-diazolesensitive catalytic site. Cloning of structural genes for the three subunits of the H+-ATPase (VMA1, VMA2, andVMA3) and their nucleotide sequence determination have been accomplished, which provide greater advantages for molecular biological studies on the structure-function relationship and biogenesis of the enzyme complex. Bioenergetic aspects of the vacuole as a main, acidic compartment ensuring ionic homeostasis in the cytosol have been described.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 21 (1989), S. 359-373 
    ISSN: 1573-6881
    Schlagwort(e): Cyrochromec oxidase ; kinetics ; subunit composition ; mitochondrially synthesized polypeptides ; Euglena gracilis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Cytochromec oxidase was purified from mitochondria ofEuglena gracilis and separated into 15 different polypeptide subunits by polyacrylamide gel electrophoresis. All 15 subunits copurify through various purification procedures, and the subunit composition of the isolated enzyme is identical to that of the immunoprecipitated one. Therefore, the 15 protein subunits represent integral components of theEuglena oxidase. In anin vitro protein-synthesizing system using isolated mitochondria, polypeptides 1–3 were radioactive labeled in the presence of [35S]methionine. This further identifies these polypeptides with the three largest subunits of cytochromec oxidse encoded by mitochondrial DNA in other eukaryotic organisms. By subtraction, the other 12 subunits can be assigned to nuclear genes. The isolatedEuglena oxidase was highly active withEuglena cytochromec 558 and has monophasic kinetics. Using horse cytochromec 550 as a substrate, activity of the isolated oxidase was rather low. These findings correlate with the oxidase activity of mitochondrial membranes. Again, reactivity was low with cytochromec 550 and 35-fold higher with theEuglena cytochromec 558. The data show that the cytochromec oxidase of the protistEuglena is different from other eukaryotic cytochromec oxidases in number and size of subunits, and also with regard to kinetic properties and substrate specificity.
    Materialart: Digitale Medien
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  • 16
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 21 (1989), S. 621-632 
    ISSN: 1573-6881
    Schlagwort(e): ATPase ; [H+]-ATPase ; proton transport ; Neurospora crassa ; Saccharomyces cerevisiae ; Schizosaccharomyces pombe
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract The fungal plasma membrane contains a proton-translocating ATPase that is closely related, both structurally and functionally, to the [Na+, K+]-, [H+, K+]-, and [Ca2+]-ATPases of animal cells, the plasma-membrane [H+]-ATPase of higher plants, and several bacterial cation-transporting ATPases. This review summarizes currently available information on the molecular genetics, protein structure, and reaction cycle of the fungal enzyme. Recent efforts to dissect structure-function relationships are also discussed.
    Materialart: Digitale Medien
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 6 (1989), S. 1032-1038 
    ISSN: 1573-904X
    Schlagwort(e): kinetics ; rate constants ; antibiotics ; adduct formation ; equilibrium
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The interaction of Teicoplanin, a glycopeptide antibiotic, with dextrose in aqueous solution has been investigated. The equilibrium concentrations of the adduct formed by the interaction of the dextrose aldehyde and the Teicoplanin amino group is shown to be directly related to the concentration of the dextrose and is thought to be inversely proportional to the hydrogen ion concentration. It was also found that phosphate ion catalyzed the reverse reaction. Approximately 30 days were required to reach equilibrium a 4°C, while equilibrium was established in about 7 days at room temperature. The reaction is reversed with dilution and the rate of the reverse reaction is two to three times faster-than expected when phosphate ion is present at 0.05 M. From the temperature dependence of the rate constants, the activation energies for the various reactions were determined to be in the range 67–80 kjoules (16–19 kcal)/mol.
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  • 18
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 6 (1989), S. 210-215 
    ISSN: 1573-904X
    Schlagwort(e): lipid emulsion ; kinetics ; prostaglandin E1 ; interface
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The overall dehydration kinetics of prostaglandin El (PGE1) in a lipid emulsion at 35°C were found to fit a model whereby the k apparent measured at each pH is simply the sum of the product of the fraction of the PGE1 at the interface,f i, and the rate constant at the interface, k i, plus the product of the fraction of the PGE1 in the aqueous phase,f aq, and the rate constant in the aqueous phase, k aq. The values for f i and f aq were reported earlier as a function of pH at 35°C. The k aq and k apparent were experimentally determined as a function of pH at 35°C. The k i was indirectly determined from the stability data in the emulsion. Microscopic rate constants for dehydration of PGE1 in the aqueous phase and interface at 35°C were estimated from the experimental data. Based on the kinetic evaluation performed, it appears that the dehydration kinetics might be manipulated by the addition of charged surface active agents.
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  • 19
    ISSN: 1573-904X
    Schlagwort(e): pancreatic lipase ; lipase ; lipolysis ; triglycerides ; kinetics ; mechanism ; calcium ; bile salts ; lecithin ; emulsions
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Lecithin-stabilized triglyceride emulsions are subject to hydrolysis by pancreatic lipase. The time profiles of these reactions are characterized by a lag-phase and a zero-order phase. Lag phases are more pronounced with long-chain triglycerides. Ca2+ is effective in reducing the lag-phase and activating lipase. Kinetic analysis of the reactions suggests that, like previous findings by others, taurodeoxycholate (TDC) micellar solutions combine with the lipase–colipase complex to form another catalytically active enzyme form. This enzyme form exhibits reduced activity in the absence of Ca2+. In the presence of Ca2+ the mixed micelle–lipase complex becomes more active and opens a new pathway for lipolysis. It is suggested that this enzyme form can bind more easily to interfaces with different physicochemical properties. Under these conditions, Ca2+ activates the lipolysis of short-, medium-, and long-chain triglycerides by a similar mechanism. Maximum activities were measured in the presence of approximately 6 mM TDC and 30 mM Ca2+. The experimental conditions approximate the physiological conditions in the gastrointestinal tract since all of the factors studied here have been reported to be necessary for in vivo lipolysis and/or absorption of triglycerides. A mechanistic model for lipolysis in the presence of Ca2+ and the bile salt TDC is proposed which accounts for most of the experimental observations in a quantitative manner.
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  • 20
    ISSN: 1573-904X
    Schlagwort(e): microcalorimetry ; Lovastatin ; decomposition ; thermodynamics ; oxidation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The application of heat conduction calorimetry to the determination of decomposition mechanisms and rates for drugs is shown to be a rapid and generally useful method. The application of the method to determine the nature of the decomposition reaction, sources of systematic errors in the method, the equations relating the calorimetric signal to the kinetics of the reaction, and some examples of results are presented and discussed.
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 266 (1988), S. 958-964 
    ISSN: 1435-1536
    Schlagwort(e): a-Se colloids ; photoadsorption ; kinetics ; activation energy ; compensation effect
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract In this study, a model is developed to explain in microscopic terms the results obtained from thermally activated photoadsorption experiments in a-Se colloids. The observed compensation effect can be described for two different cases. At low efficiency adsorption, the process is controlled by the potential at the boundary layer. In the high efficiency adsorption case, the process is controlled by diffusion transport.
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  • 22
    Digitale Medien
    Digitale Medien
    Springer
    Microchimica acta 94 (1988), S. 277-278 
    ISSN: 1436-5073
    Schlagwort(e): kinetics ; FT-IR ; temporal resolution
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A system for performing gas-phase rapid scanning Fourier transform infrared time-resolved Spectrometry (FT-IR/TRS) has been evaluated. This technique can be applied to the study of the lifetimes and reactivity of transient species and can provide detailed information regarding reaction rate constants. Temperature-jump experiments have been initiated and preliminary results are presented.
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Microchimica acta 94 (1988), S. 323-328 
    ISSN: 1436-5073
    Schlagwort(e): FTIR spectroscopy ; kinetics ; polymers ; rheo-optics ; variable-temperature measurements
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The rapid-scanning capability of FTIR instrumentation has revitalized the field of vibrational spectroscopy in polymer research and will be discussed with reference to the study of polyurethane kinetics, the temperature dependence of hydrogen bonding in polyamide 6 and strain-induced crystallization in a polydimethylsiloxane elastomer.
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  • 24
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 8 (1988), S. 101-110 
    ISSN: 1572-8986
    Schlagwort(e): Plasma ; laser ; diagnostics ; hydrocarbons ; free radicals ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The dynamics of the formation and decay of excited hydrogen during a pulse discharge in methane at a pressure of 200 Pa and energy density of 0.05 J/cm3 has been studied. The population of hydrogen in the n=2 state was monitored by the laser absorption method. The time constant of the decay of the excited hydrogen was measured to be 95±15 ns. The concentration of free electrons reached a maximum value of 7×1014 cm−3, and the time constant of their recombination was 220±50 ns. The formation of appreciable amounts of atomic hydrogen in the ground state during the discharge, H(n=1)〉1016 cm−3, was estimated on the basis of a kinetic model.
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  • 25
    ISSN: 1432-1424
    Schlagwort(e): vacuole ; lipid bilayer ; K-channel ; single channel ; DIDS ; yeast ; Saccharomyces cerevisiae ; Ca2+ activation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary A voltage-dependent and Ca2+-activated cation channel found in the vacuolar membrane of the yeast,Saccharomyces cerevisiae, was incorporated into planar lipid bilayer and its gating characteristics were studied at the macroscopic and single-channel levels. The open-channel probability at steady state, which was estimated by the macroscopic current measurement, gave a maximum value at −10 mV and decreased in a graded fashion as the voltage became more positive or more negative. The steady-state voltage dependence was explained by assuming two independent gates, which had different rate constants and opposite voltage dependence. The fast-responding gate opened when the voltage of thecis side (the side to which the vesicles were added) was made more negative and the slow-responding gate behaved in the opposite direction. Relatively high concentrations of Ca2+, about 1mm, were required on thecis side for opening the slow gate in a voltage-dependent manner. DIDS increased the open-channel probability of the fast gate when added to thecis side, but was ineffective on the slow gate.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    The journal of membrane biology 102 (1988), S. 225-234 
    ISSN: 1432-1424
    Schlagwort(e): erythrocytes ; valinomycin ; protonophore ; CCCP ; permeability ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary A transport model for translocation of the protonophore CCCP across the red cell membrane has been established and cellular CCCP binding parameters have been determined. The time course of the CCCP redistribution across the red cell membrane, following a jump in membrane potential induced by valinomycin addition, has been characterized by fitting values of preequilibrium extracellular pHvs. time to the transport model. It is demonstrated, that even in the presence of valinomycin, the CCCP-anion is “well behaved,” in that the translocation can be described by simple electrodiffusion. The translocation kinetics conform to an Eyring transport model, with a single activation energy barrier, contrary to translocation across lipid bilayers, that is reported to follow a transport model with a plateau in the activation energy barrier. The CCCP anion permeability across the red cell membrane has been calculated to be close to 2.0×10−4 cm/sec at 37°C with small variations between donors. Thus the permeability of CCCP in the human red cell membrane deviates from that found in black lipid membranes, in which the permeability is found to be a factor of 10 higher.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 266 (1988), S. 1102-1109 
    ISSN: 1435-1536
    Schlagwort(e): Hydrogenbonds ; reversiblenetworks ; complexformation ; complexdecomplexation ; kinetics ; viscoelasticity ; influence oftemperature
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The dynamics of hydrogen bond complex formation between functional groups which are attached to a polymer chain, is studied in the molten state. The concentration of complexes in the thermodynamic equilibrium is distorted by the application of a large oscillatory strain in the nonlinear viscoelastic regime. The relaxation back to the thermodynamic equilibrium is studied as a function of the temperature in the linear viscoelastic regime. From the mechanical response the kinetic analysis can be performed using a modified Doi-Edwards theory. Using the equilibrium constants obtained from IR-spectroscopy, the rate constants for complex formation and decomplexation are obtained. The temperature dependence is equivalent to the temperature dependence of the zero shear viscosity which implies that complex formation is a diffusion-controlled process.
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  • 28
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 5 (1988), S. 86-91 
    ISSN: 1573-904X
    Schlagwort(e): acute tolerance ; bumetanide ; kinetics ; dynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bumetanide was administered intravenously to four mongrel dogs as a bolus of 8.7 µg/kg, immediately followed by a constant-rate infusion of 0.35 µg/min/kg at 0.036 ml/min. Treatment A consisted of a 90-min equilibration period and first hour (Phase I) of study in which animals were maintained under euvolemic conditions. During the subsequent 3 hr of Treatment A (Phase II), animals were maintained under hydropenic conditions. These experiments were then repeated 1 week later (Treatment B) with the temporal aspects of hydration reversed (Phase III, hydropenia; Phase IV, euvolemia). Serial plasma and urine samples were assayed for bumetanide by high-performance liquid chromatography (HPLC) and for sodium by flame photometry. The bumetanide excretion rate was not significantly different during the 4 hr of Treatment A, although minor differences were observed between Phase III and Phase IV of Treatment B. The sodium excretion rate showed significant differences between euvolemic and hydropenic conditions of both treatments. A two- to threefold difference in the sodium excretion rate persisted even when slight differences (〈20%) in bumetanide excretion rates were taken into account. These results demonstrate that an acute tolerance does develop to constant-rate infusions of bumetanide when inadequate fluid and electrolyte replacement occurs and that this tolerance can be reversed by rehydration.
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 265 (1987), S. 58-64 
    ISSN: 1435-1536
    Schlagwort(e): Polymerisation ; emulsion ; styrene ; methylmethacrylate ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The dependence of emulsion polymerisation rates on a number of important parameters is considered. Attention is paid to the use of seeded emulsion systems for the evaluation of radical desorption coefficients (k o). Experimental conditions are shown to be important. When the average number of radicals per particle is low, large changes in the rate coefficient for chain termination do not have a large effect on the kinetics. With styrene and methylmethacrylate, radical re-absorption by the polymer particles is shown to be important and radical capture efficiences can be high. Consistency is established between the results of a number of workers and values fork o are shown to be lower than those calculated from chain transfer rates.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Molecular and cellular biochemistry 76 (1987), S. 45-54 
    ISSN: 1573-4919
    Schlagwort(e): DNA methyltransferase ; hemimethylated DNA ; kinetics ; affinity chromatography ; (rat liver)
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Medizin
    Notizen: Abstract DNA substrate analogs were constructed from poly(dC-dG), M13, and XP12 DNA which do not contain a mixture of types of methylation sites. These were used to distinguish different kinetic mechanisms for maintenance and de novo methylation using a highly purified rat liver DNA (cytosine-5)-methyltransferase (DMase−) preparation. De novo methylation on single (ss) and double-stranded (ds) DNA was found to obey Michaelis-Menten kinetics while methylation of hemimethylated sites showed differences depending on size of the hemimethylated region. On long stretches analogous to maintenance methylation of newly replicated DNA, saturation could not be achieved and the kinetics showed non-ideal positive cooperative kinetics, while short stretches showed non-Michaelis-Menten kinetics and rapid saturation. Two types of DMase-DNA complexes could be distinguished by means of affinity chromatography on DNA-agarose matrices and in preincubation assays. The later complex, which is engaged in methyl group turnover, exhibited enhanced stability. The competitiveness of variously configured DNAs was found to parallel the stability of complex formation, e.g., ss, hemi- and ds DNA, respectively. In studies utilizing 5-bromodeoxyuridine, the thymine analog left the basic reaction mechanisms unchanged but increased the km and S0.5 while reducing the velocity of these reactions.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    The protein journal 6 (1987), S. 413-429 
    ISSN: 1573-4943
    Schlagwort(e): lactate dehydrogenase isoenzymes ; lactate-to-pyruvate reaction ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In order to evaluate the functional differences that may exist in human lactate dehydrogenase (LDH) isoenzymes widely used for clinical examination the kinetic and thermodynamic properties of the lactate to pyruvate reaction that they catalize were examined. Small but significant differences in the kinetic properties of the three isoenzymes were observed. The difference in the rate constants might affect the activity measurement of the individual isoenzyme as the initial velocity for the L-P reaction catalyzed will not be the same for an equal amount of enzyme. Equilibrium constants for the overall reaction in the presence and absence of pyruvate have been determined. On the basis of transition-state theory, the standard enthalpy and free-energy changes for formation of ternary activated complex were positive, while the standard entropy change was negative. Although the standard free-energy change was the same for activation by the three isoenzymes, the enthalpy and entropy changes for the LDH-3-catalyzed reaction were different from the respective values for others. A large positive value for the free-energy change and a negative value for the entropy change indicated unfavorable production of the activated complex (K infeq. sup╪ =1.89×10-16). The enzyme appears to stabilize and retain the activated complex until it dissociates into the products.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 4 (1987), S. 392-397 
    ISSN: 1573-904X
    Schlagwort(e): angiotensin-converting enzyme (ACE) inhibitor ; RS-10085 ; degradation ; kinetics ; products ; diketopiperazine ; peptides
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The degradation kinetics, products, and mechanisms of RS-10085(1), 2-[2-(l-ethoxycarbonyl)-3-phenylpropyl]amino-l-oxopropyl]-6,7-dimethoxy-l,2,3,4-tetrahydroisoquinoline-3-carboxylic acid(S,S,S), in aqueous solution were investigated at 40, 60, and 80°C from pH 1 to pH 13. Pseudo-first-order kinetics were observed throughout the pH range studied and the log(rate)−pH profiles reflected four kinetic processes (k o, k′o, k″o, and k OH) as well as the two pKa's of 1. Excellent (〉98%) mass balance was obtained through products 2–5. At pH 4 or below, intramolecular cyclization leading to diketopiperazine 5 accounted for greater than 93% of the observed neutral- or water-catalyzed processes (k o and k′o). At pH levels greater than 5, hydrolysis giving 2 predominated and was responsible for the observed neutral- or water-catalyzed (k″o) and specific base-catalyzed (k OH) kinetic processes. Some epimerization leading to the S,S,R drug isomer (4) was also observed at pH levels greater than 7. The relative acidity of the protons at the three chiral centers of 1 was qualitatively compared and was used to explain the observed specificity in epimerization.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Pharmaceutical research 4 (1987), S. 379-384 
    ISSN: 1573-904X
    Schlagwort(e): acute tolerance ; bumetanide ; kinetics ; dynamics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bumetanide was administered intravenously to four mongrel dogs, in a random crossover fashion, at doses of 0.05 mg/kg (I), 0.15 mg/kg (II), and 0.5 mg/kg (III) where urinary losses were replaced with lactated Ringer's solution at 1.5 ml/min (hydropenic conditions) or at a dose of 0.5 mg/kg (IV) where urinary losses were replaced with lactated Ringer's solution isovolumetrically (euvolemic conditions). Serial plasma and urine samples were assayed for bumetanide by high-performance liquid chromatography (HPLC) and for sodium by flame photometry. There were no significant differences in the pharmacokinetic parameters of bumetanide among Treatments I–IV. The dynamic parameters E max (maximum effect attributable to the drug) and s (slope factor) were not different between treatments. However, a consistent, demonstrable increase in ER50 (urinary excretion rate of drug producing 50% of E max) was observed among Treatments I (2.34 µg/min), II (3.92 µg/min), and III (6.54 µg/min); also, a significant decrease in ER50 was observed between Treatment III (6.54 µg/min) and Treatment IV (2.66 µg/min). These results show that hydration status has a marked effect on natriuretic and diuretic response and that tolerance can rapidly develop within a single intravenous dose of bumetanide.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 265 (1987), S. 193-205 
    ISSN: 1435-1536
    Schlagwort(e): Poly(TMPS) ; in situ ; SAXS ; crystallization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The isothermal crystallization kinetics of poly(TMPS) has been measured by ISSAXS and results obtained for a molecular weight fraction (21,000) below the critical entanglement molecular weight (25,000) and another one above it (371,000). The SAXS intensity vs. time curves suggest that a single transformation mechanism exists. The SAXS long period is independent of crystallization time for both poly(TMPS) fractions. However the interlamellar thickness contribution to the long period is dependent upon molecular weight and crystallization temperature, increasing with temperature and molecular weight. The crystallite contribution also increases over the range studied. Both fractions exhibit a significant, but reversible decrease in thickness on cooling the sample from the crystallization temperature to room temperature and recyling again. The change is more pronounced for 371,000 specimen in keeping with its lower crystallinity. The path dependence of lamellar dimensions has significant implications in the morphological characterization of polymers annealed or crystallized at one temperature and then measured at another one.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 74 (1987), S. 55-63 
    ISSN: 1435-1536
    Schlagwort(e): Triplet energy transfer ; micelle ; solubilization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract Triplet energy transfer from 9-methylanthracene to azulene or guajazulene has been used to probe the migration of azulenes between micelles in aqueous solution. The migration of the hydrophobic solutes between small ionic and nonionic micelles had the temperature dependence expected for a process controlled by diffusion through the intermicellar solution, although the rate in some cases was substantially less than calculated from the Smoluchowski equation. Under conditions in which the micelles grow into large, probably rod-like structures, there are severe difficulties in separating the inter- and intramicellar deactivation processes. The intermicellar migration was enhanced under these conditions, in cetyltrimethylammonium surfactants on addition of chlorate ions, and in hexaethylene glycol dodecylether at temperatures approaching the cloud-point. The mechanism of this migration is discussed and compared with pertinent results from micelle relaxation kinetics and surfactant self-diffusion measurements.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 5 (1987), S. 385-395 
    ISSN: 1573-1111
    Schlagwort(e): Nitrogen monoxide ; ESR spectroscopy ; disproportionation reaction ; CaHY-type zeclite ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract An ESR spectroscopic study of adsorbed NO on CaHY-type zeolite was carried out and the kinetics are discussed on the basis of a mechanistic model of the disproportionation reaction. An amount of NO less than the amount of Ca2+ distributed in Site II of the faujasite structure was admitted onto the sample maintained at 373 K. ESR spectra were recorded at room temperature. The spectra consisted of well-resolved signals. It is proposed that NO molecules on CaHY-type zeolite have two kinds of adsorption patterns. The initial formation of N2O may be expressed by the following reactions: $$[ ] + NO\mathop \rightleftharpoons \limits_{}^{K_1 } [NO],[NO] + NO\mathop \rightleftarrows \limits_{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 }^{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {K} _2 } [N_2 O_2 ],[N_2 O_2 ] + NO\mathop \to \limits_{}^{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {K} _3 } [NO_2 ] + N_2 O,$$ where [], [NO] and [N2O2] denote vacant adsorption, NO adsorption, and N2O2 adsorption sites, respectively. A rate equation for N2O appearance (α) has been derived by a steady state approximation: $$\alpha = \frac{{\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 K_1 K_2 P^3 }}{{1 + (K_1 + \overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 /\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 )P + K_1 (K_2 + \overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\rightharpoonup}$}} {k} _3 /\overset{\lower0.5em\hbox{$\smash{\scriptscriptstyle\leftharpoonup}$}} {k} _2 )P^2 }},$$ WhereP is the pressure of NO. The rate equation was used to explain the kinetic results of the disproportionation of NO.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 5 (1987), S. 709-716 
    ISSN: 1573-1111
    Schlagwort(e): Cyclodextrin ; rhodamine B ; equilibrium ; kinetics ; temperature-jump
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A UV/visible spectrophotometric temperature-jump study of the inclusion of the rhodamine B zwitterion (RB) by β-cyclodextrin (βCD) to form a 1:1 complex (RB·βCD) in aqueous 1.00 mol dm−3 NaCl at pH 6.40 and 298.2 K yields:k 1=(1.3±0.2)×108 dm3 mol−1 s−1,k −1=(2.2±0.5)×104 s−1, andK 1=(5.9±2.3)×103 dm3 mol−1 for the equilibrium: $${\text{RB + }}\beta {\text{CD}}{\text{RB}} \cdot \beta {\text{CD}} K_1 $$ Under the same conditions the dimerization of RB: $${\text{2}} {\text{RB}}({\text{RB}})_2 K_d $$ is characterized byK d =(1.8±1.0)×103 dm3 mol−1. The interaction of RB with αCD and γCD is weaker than with βCD, and is discussed in terms of the relative sizes of RB and the cyclodextrin annulus. Comparisons are made with the inclusions of other dyes by cyclodextrins.
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  • 38
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 15 (1986), S. 221-229 
    ISSN: 1572-8927
    Schlagwort(e): Ultrasonics ; kinetics ; aqueous solution ; triethylene glycol monobutyl ether
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The ultrasonic absorption from 6.5 to 220 MHz and velocities at 2.5 MHz have been measured in aqueous solution of triethylene glycol monobutyl ether as a function of concentration at 25°C. A single relaxational excess absorption, observed from 0.60 to 2.5 mol-dm−3, is attributed to a perturbation of an equilibrium associated with solute-solvent interaction. Rate constants for the forward and reverse processes have been determined from the concentration dependence of the relaxation frequency, and the influence on the water structure by an addition of the solute has been considered. Solution densities were also measured in order to obtain the expansivity of the solution. The standard volume and enthalpy changes of the reaction have been estimated from the concentration dependence of the maximum excess absorption per wave length. A linear relationship between the number of oxyethylene groups and the free energy change between bonded water and nonbonded water is established.
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  • 39
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 29 (1986), S. 529-534 
    ISSN: 1432-1041
    Schlagwort(e): pethidine ; epidural injections ; pain scores ; kinetics ; spinal cord
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Twenty-one patients who had undergone total hip replacement were randomly assigned to one of three groups in order to compare a single dose of 1 mg/kg of pethidine im (I) and 20 mg (II) or 60 mg of extradural pethidine (III) in a double-blind design. The degree of analgesia, the adverse effects, and the kinetics were studied for 18 h. Pain was monitored using a visual analogue scale (VAS). Supplementary doses of oxycodone if required were given no earlier than 0.75 h after pethidine. Plasma concentrations of pethidine were measured with gas chromatography mass spectrometry (GCMS). Hypoalgesia to pin prick test was evaluated. Low pain scores were observed in the extradural groups between 0.25 and 1.5 h after the dose. A significant difference in pain score compared with the im group was found after the higher extradural dose only between 0.5 and 1 h (p〈0.05). The area under the curve (AUC) of pain score versus time (0–18 h) was not significantly different between groups. The recorded adverse effects were minor in all three groups. The terminal half-lives and plasma clearances of pethidine, and the time to peak concentration were not different between the groups. Single patients in the extradural groups showed hypoalgesia to pin prick in parallel to the effect. The present study shows that extradural pethidine produces shortlived analgesia, in contrast to the long-lasting effect of morphine found in other studies.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 6 (1986), S. 429-436 
    ISSN: 1572-8986
    Schlagwort(e): Plasma ; laser ; diagnostics ; free radicals ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract The plasma of a pulse discharge (0.05 J/cm3) in methane at low pressure (200 Pa) is studied. The dynamics of formation and decay of C2(a3IIu, v″=0) is monitored using a stroboscopic laser absorption method. It was found that substantial amounts of C2, 1015 cm−3, arise with a 1-µs delay after the current pulse.
    Materialart: Digitale Medien
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  • 41
    ISSN: 1573-4935
    Schlagwort(e): Candida utilis ; cellulase ; DNAse ; β-glucuronidase ; Hansenula jadinii ; protoplast ; Saccharomyces cerevisiae ; Schizosaccharomyces pombe ; spheroplast ; yeast
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Efficient preparation of spheroplasts fromCandida utilis, Saccharomyces cerevisiae, andSchizosaccharomyces pombe, using a purified mixture of enzymes fromTrichoderma harzianum, is described. Limitations of other methods, and differences between yeasts are demonstrated.
    Materialart: Digitale Medien
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    The journal of membrane biology 90 (1986), S. 67-87 
    ISSN: 1432-1424
    Schlagwort(e): cotransport ; kinetics ; reaction kinetic model ; dual isotherm ; random binding ; slip
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Summary Solute uptake in many cells is characterized by a series of additive Michaelis-Menten functions. Several explanations for these kinetics have been advanced: unstirred layers, transport across more than one membrane, effects of solute concentration on membrane potential, numerous carrier systems. Although each of these explanations might suffice for individual cases, none provides a comprehensive basis for interpretation of the kinetics. The most common mechanism of solute absorption involves cotransport of solute with a driver ion. A model is developed in which solute and driver ion bind randomly to a membrane-bound carrier which provides a single transmembrane pathway for transport. The kinetic properties of the model are explored with particular reference to its capacity to generate additive Michaelian functions for initial rate measurements of isotopic solute influx. In accord with previous analysis of ordered binding models (Sanders, D., Hansen, U.-P., Gradmann, D., Slayman, C.L. (1984)J. Membrane Biol. 77:123), the conventional assumption that transmembrane transit rate-limits transport has not been applied. Random binding carriers can exhibit single or multiple Michaelian kinetics in response to changing substrate concentration. These kinetics include high affinity/low velocity and low affinity/high velocity phases (so-called “dual isotherms”) which are commonly observed in plant cells. Other combinations of the Michaelis parameters can result incis-(substrate) inhibition. Despite the generality of the random binding scheme and the complexity of the underlying rate equation, a number of predictive and testable features emerge. If external driver ion concentration is saturating, single Michaelian functions always result and increasing internal substrate concentration causes uncompetitive inhibition of transport. Numerical analysis of the model in conditions thought to resemble those in many experiments demonstrates that small relative differences in a few key component rate constants of the carrier reaction cycle are instrumental in generation of dual isotherms. The random binding model makes the important prediction that the contributions of the two isotherms show opposing dependence on external concentration of driver ion as this approaches saturation. In the one case in which this dependence has been examined experimentally, the model provides a good description of the data. Charge translocation characteristics of the carrier can be determined from steady-state kinetic data on the basis of the response of substrate flux to modulation of internal driver ion concentration. The application of the model to dual isotherm kinetics is discussed in relation to “slip” models of cotransport, in which the carrier is assumed to have the capability to transport substrate alone or with the driver ion. A method for distinguishing between the two models is suggested on the basis of measurement of charge/solute transport stoichiometry as a function of external driver ion concentration.
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    Biogeochemistry 2 (1986), S. 149-161 
    ISSN: 1573-515X
    Schlagwort(e): Microbial manganese(II) oxidation ; manganese(II) oxidation ; kinetics ; bacteria ; O2H2S interface 04
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract A great number of important chemical reactions that occur in the environment are microbially mediated. In order to understand the kinetics of these reactions it is necessary to develop methods to directly measure in situ reaction rates and to develop models to help elucidate the mechanisms of microbial catalysis. The oxidation of Mn(II) in a zone above the O2/H2S interface in Saanich Inlet, B.C., Canada is one such reaction. We present here a method by which in situ rates of microbial Mn(II) oxidation are measured and a model based on our experimental results to describe the general mechanism of Mn(H) oxidation. We propose a two step process in which Mn(II) is first bound by a site on the bacterial surface and then oxidized. The model is analogous to the Langmuir isotherm model for surface catalyzed gas reactions or the Michaelis-Menten model for enzyme kinetics. In situ Mn(II) oxidation rates were measured during five cruises to Saanich Inlet during the summers of 1983 and 1984. We use the model to calculate the apparent equilibrium binding constant (Ks ≈ 0.18 μM), the apparent half saturation constant for biological Mn(H) oxidation (Km = 0.22 to 0.89 μM), the maximum rate of Mn(II) oxidation (Vmax = 3.5 to 12.1 nM·h-1) and the total microbial surface binding site concentration (Σ E ≈ 51 nM). Vmax for Mn(II) oxidation agrees with the rates calculated from the value of the flux of Mn(II) to the oxidizing zone using the Mn(II) gradient and estimates of the eddy diffusion coefficient. This consistancy verifies our methodology and indicates that the rate of Mn(II) oxidation is nearly equal to the (Vmax for the reaction. We conclude that in this environment the Mn(II) oxidation rate is more a function of the total number of surface binding sites than the Mn(H) concentration.
    Materialart: Digitale Medien
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 18 (1986), S. 71-91 
    ISSN: 1573-6881
    Schlagwort(e): Phospholipid transfer protein ; phosphatidylcholine ; phosphatidyllinositol ; exchange ; net transfer ; lipid-protein interactions ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Phospholipid transfer proteins are generally localized in the cytosolic fraction of cells and are capable of catalyzing the flux of phospholipid molecules among membranes. Artificial membranes also participate in protein-catalyzed phospholipid movements. In this review the major phospholipid transfer proteins are discussed with respect to their phospholipid substrate specificity and the contributions of membrane physical properties to this process. The phenomenon of net transfer of phospholipids is described. The use of various kinetic approaches to the study of these catalysts is reviewed. A detailed consideration of the distinct phospholipid binding and membrane interaction domains of one phospholipid transfer protein is presented. Finally, some recent applications of phospholipid transfer proteins to the examination of membrane structure and function and further directions for the continued research activity with this class of proteins are summarized.
    Materialart: Digitale Medien
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inclusion phenomena and macrocyclic chemistry 4 (1986), S. 325-331 
    ISSN: 1573-1111
    Schlagwort(e): Aluminophosphate ; molecular sieves ; crystallization ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A member of the novel family of crystalline microporous aluminophosphates, AlPO4-12, was synthesized by hydrothermal crystallization using different aluminum-containing compounds. Three new crystalline phases were obtained by varying the composition of the reaction mixture. The effect of the synthesis conditions on the hudrothermal process and the kinetics of crystallization are discussed. The apparent activation energies obtained for AlPO4-12 are 20.9 and 14.6 kcal/mol for nucleation and crystallization, respectively. The adsorption isotherms of one AlPO4-12 product were measured.
    Materialart: Digitale Medien
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    Journal of atmospheric chemistry 4 (1986), S. 241-251 
    ISSN: 1573-0662
    Schlagwort(e): Free radical reactions ; kinetics ; product distribution ; methane oxidation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract Formation of methoxy (CH3O) radicals in the reaction (1) CH3O2+NO→CH3O+NO2 at 298 K has been observed directly using time resolved LIF. The branching ratio % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaeqOXdyMaae% 4qaiaabIeadaWgaaWcbaGaae4maaqabaGccaqGpbGaaeiiaiaabIca% ieqacaWF9aGaa8hiaiaa-nbicaWFGaGaeuiLdqKaai4waiaaboeaca% qGibWaaSbaaSqaaiaabodaaeqaaOGaae4taiaac2facaWFVaGaeuiL% dqKaai4waiaaboeacaqGibWaaSbaaSqaaiaabodaaeqaaOGaae4tam% aaBaaaleaacaqGYaaabeaakiaac2facaqGPaaaaa!4E31!\[\phi {\rm{CH}}_{\rm{3}} {\rm{O (}} = -- \Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}]/\Delta [{\rm{CH}}_{\rm{3}} {\rm{O}}_{\rm{2}} ]{\rm{)}}\] has been determined by quantitative cw-UV-laser absorption at 257 nm of CH3O2 and CH3ONO, the product of the consecutive methoxy trapping reaction (2) % MathType!MTEF!2!1!+-% feaafeart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaae4qaiaabI% eadaWgaaWcbaGaae4maaqabaGccaqGpbacbeGaa83kaiaa-bcaieaa% caGFobGaa43taiaa+bcacaGFOaGaa83kaiaa+1eacaGFPaGaa4hiai% abgkziUkaabccacaqGdbGaaeisamaaBaaaleaacaqGZaaabeaakiaa% b+eacaqGGaGaaeOtaiaab+eacaqGGaGaa4hkaiaa-TcacaGFnbGaa4% xkaiaa+5cacaGFGaGaa4hiaiabeA8aMnaaBaaajqwaacqaaiaaboea% caqGibWaaSbaaKazcaiabaGaae4maaqabaqcKfaGaiaab+eaaSqaba% aaaa!55AC!\[{\rm{CH}}_{\rm{3}} {\rm{O}} + NO ( + M) \to {\rm{ CH}}_{\rm{3}} {\rm{O NO }}( + M). \phi _{{\rm{CH}}_{\rm{3}} {\rm{O}}} \] is found to be (1.0±0.2). The rate constant k 1 is (7±2) 10-12 cm3/molecule · s in good agreement with previous results.
    Materialart: Digitale Medien
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  • 47
    Digitale Medien
    Digitale Medien
    Springer
    Biogeochemistry 2 (1986), S. 313-328 
    ISSN: 1573-515X
    Schlagwort(e): soil organic sulfur ; mineralization ; reaction rates ; kinetics ; immobilization ; soil adsorption ; sulfate ; first-order ; michaelis-menten
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract Transformations of organic and inorganic S in two forested Spodosols from the Hubbard Brook Experimental Forest, New Hampshire and the Huntington Forest in the Adirondack Mts. of New York were investigated using laboratory35SO4 2- incorporation experiments. Sulfur transformations were modeled as a set of three reversible, first-order reactions in which soluble SO 4 2- is converted to adsorbed SO 4 2- , ester sulfate and carbon-bonded S. Reaction rate contants for35SO 4 2- adsorption/desorption and immobilization reactions involving ester sulfate and carbon-bonded S were determined using a fifth order Runge-Kutta-Fehlberg integration routine combined with least squares fitting. Model simulations were able to account for over 93% of the variation in the distribution of35S in S fractions. A hypothetical application of immobilization rate constants to field situations at the Hubbard Brook Experimental Forest suggests that large quantities of S cycle through organic forms in Northern Hardwood Forest Ecosystems.
    Materialart: Digitale Medien
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  • 48
    ISSN: 1435-1536
    Schlagwort(e): Phospholipid bilayer ; kinetics ; laser temperature jump ; phase transition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The iodine-laser temperature-jump technique has been used to investigate the main phase transition in single shell vesicles of dimyristoylphosphatidylcholine. The probe molecules DPH and TMA-DPH were incorporated into the lipid bilayer and laserT-jump experiments with turbidity and flourescence polarization detection were performed. We found three well separated relaxation processes between 5 μs and 10 ms. The relaxation signals showed strong cooperativity in the relaxation times as well as in their corresponding amplituedes. We attributed the relaxation to the formation and dissolution of clusters of different order inside the bilayer.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 49
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 29 (1985), S. 251-253 
    ISSN: 1432-1041
    Schlagwort(e): paracetamol ; antacids ; acetaminophen ; bioavailability ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The effect of two antacids on the bioavailability of paracetamol has been investigated in 12 young healthy volunteers. Following a random cross over design, each subject swallowed, on three separate occasions, one weak apart, 500 mg paracetamol alone, or together with two different aluminium hydroxide, magnesium hydroxide preparations (Dimalan and Maalox). Plasma paracetamol levels were measured by HPLC. The bioavailability of paracetamol was not altered by either antacid, but they both delayed the time to peak plasma concentration (0.85 h; 1.43 h; 1.25 h, without antacid, with Dimalan and with Maalox respectively). The peak plasma concentration was not affected by concurrent antacid administration.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 28 (1985), S. 163-169 
    ISSN: 1432-1041
    Schlagwort(e): indomethacin ; platelet aggregation ; prostanoids ; plasma concentration ; arachidonic acid ; thromboxane B2 ; 6-keto-prostaglandin F1α ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary A single oral dose of indomethacin 1 mg/kg was given to 6 male and 6 female volunteers. The formation of thromboxane B2 (TXB2) and 6-ketoprostaglandin F1α (6-keto-PGF1α) in clotting whole blood was measured by radioimmunoassay, and platelet aggregation induced by archidonic acid (AA) was measured with a plasma aggregometer. The results were related to the concomitant plasma concentration of indomethacin. The maximum plasma concentration ranged between 3.24 and 8.11 µg/ml and the elimination half-life between 4 and 11 h. Formation of the prostanoids was reversibly inhibited, with maximum suppression when the drug concentration in plasma exceeded 0.5–1.0 µg/ml; the IC50 was approximately 0.1 µg/ml. Platelet aggregation was also reversibly inhibited. The correlation between the formation of prostanoids and the different phases of the aggregatory response to exogenous AA is discussed.
    Materialart: Digitale Medien
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  • 51
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 5 (1985), S. 293-316 
    ISSN: 1572-8986
    Schlagwort(e): Plasma chemistry ; halocarbon decomposition ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract For the case of weak feed gas decomposition, where the concentration of CCl4 exceeds those of decomposition and built-up products, the emission of CCl* is shown to originate from dissociative excitation of CCl4. With electron concentration measured independently, the kinetics of CCl4 decomposition has been extracted from the time dependence of the CCl* intensity. Supported by EPR determinations of radical concentrations in rapidly flowing CCl4 and CCl4/O2 afterglows, the primary decomposition reaction is shown to be the electron impact dissociation into CCl3 and Cl. Its rate constant (k 1=4×10−8 cm3s−1) indicates strongly that dissociative electron attachment is the main reaction channel at least at r.f. power densities just above the threshold of a self-maintaining discharge. At extremely low mean electron energies the emission of a continuum is observed, which is tentatively ascribed to the radiative CCl3-Cl recombination.
    Materialart: Digitale Medien
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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    Plasma chemistry and plasma processing 5 (1985), S. 283-291 
    ISSN: 1572-8986
    Schlagwort(e): Methane ; acetylene ; kinetics ; modeling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau , Technik allgemein
    Notizen: Abstract It is shown that it is basically possible to model plasma-chemical methane conversion using a kinetic concept regardless of the kind of plasma, i.e., the kind of activation. While the temporal plasma-chemical decomposition of methane is controlled by a first-order rate equation, the temporal product formation can be described by a set of first-order consecutive reactions. Prolonged portions of constant product concentrations in the temporal product formation curves were explained by the assumption of an equilibrium between forward and reverse reactions. The modeling revealed the special role of the re-formation of dissociated molecules.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    Biochemical genetics 23 (1985), S. 859-876 
    ISSN: 1573-4927
    Schlagwort(e): allozyme ; Cnidaria ; cline ; isozyme ; kinetics ; Metridium senile ; phosphoglucomutase ; polymorphism ; variation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract The phosphoglucomutase (Pgm) locus from populations of the sea anemone Metridium senile has three alleles in natural populations from the northeastern coast of North America. Two of the alleles exhibit clinal variation north of Cape Cod, suggesting a possible association of allele frequency with environmental temperature. This clinal pattern is reproducible and stable over at least brief periods of time. The allozymes encoded by each of the six Pgm genotypes have been partially purified and characterized. The symmetrical pH optimum for V max is pH 7.5; the apparent K m (K m app ) of glucose-1-phosphate declines monotonically as the pH increases from 6.5 to 8.5. There are no pronounced differences in heat stabilities of PGM produced by various genotypes, nor are there significant differences in specific activities. There are no differences in the sensitivity of V max to temperature. K m app values are very low for all genotypes, ranging from about 2 to 12 µm, depending upon the temperature. K m app of glucose-1-phosphate declines as the temperature is raised for all genotypes, whether the pH is held constant or allowed to vary with the temperature. Under certain conditions, there are small significant differences among genotypes in K m app values, but there is no systematic pattern to these differences. The present data provide no biochemical explanation for the maintenance of the Pgm cline by selection for functional differences under different thermal regimes.
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  • 54
    Digitale Medien
    Digitale Medien
    Springer
    Journal of pharmacokinetics and pharmacodynamics 13 (1985), S. 229-241 
    ISSN: 1573-8744
    Schlagwort(e): food effects ; propranolol ; kinetics ; dogs ; oral and intravenous doses
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The intravenous and oral dose kinetics of propranolol were studied in the dog both in a fasted state and immediately after a meal consisting of 100 g of cooked beef liver. Fifty ΜCi of3H-propranolol was administered intravenously simultaneously with a 40-mg oral dose of unlabeled propranolol. Plasma3H-propranolol was measured by specific extraction and liquid scintillation spectrometry, and unlabeled plasma propranolol was determined by gas chromatography-mass spectrometry. Feeding significantly reduced (25%) the elimination half-life and increased (52%) the systemic clearance of intravenous propranolol. The increase in the systemic clearance of propranolol after feeding was mostly due to an increase (60%) in apparent hepatic blood flow, which appeared to remain elevated for 5–7 hr. The meal had no influence on the apparent volume of distribution or plasma binding. Feeding did not affect the area under the concentration-time curve of oral propranolol, but significantly delayed the rate of oral propranolol absorption, shifting the time to reach peak plasma levels from 60 to 158 min. The results of this study suggest that feeding alters the disposition of propranolol in the dog by producing a sustained increase in hepatic blood flow.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 17 (1985), S. 375-384 
    ISSN: 1573-6881
    Schlagwort(e): Cytochromec oxidase ; kinetics ; trypsin digestion ; reconstitution ; proteoliposomes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Isolated beef heart cytochromec oxidase was reconstituted in liposomes by the cholate dialysis method with 85% of the binding site for cytochromec oriented to the outside. Trypsin cleaved specifically subunit VIa and half of subunit IV from the reconstituted enzyme. The kinetic properties of the reconstituted enzyme were changed by trypsin treatment if measured by the spectrophotometric assay but not by the polarographic assay. It is concluded that subunit VIa and/or subunit IV participate in the electron transport activity of cytochromec oxidase.
    Materialart: Digitale Medien
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    Journal of bioenergetics and biomembranes 17 (1985), S. 305-326 
    ISSN: 1573-6881
    Schlagwort(e): α-Aminoisobutyric acid ; amino acids ; brain slices ; exchange diffusion ; kinetics ; membrane transitions ; rate equations ; transport
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie , Physik
    Notizen: Abstract Rate equations for the gross influx of α-aminoisobutyric acid (AIB) into mouse cerebrum slices containing AIB have a first-order term for unsaturable concentrative influx, identical to the corresponding term for unloaded slices, and a modified Michaelis-Menten term,V′max/(1+K t /S), for saturable concentrative influx. [V′max ≡v′ L (1+K t /S), wherev′ L =saturable component of influx,S=AIB concentration in medium, andK t =Michaelis constant for unloaded slices.] Below a tissue AIB (T) of 19 µmol/g final wet weight,V′max increases linearly followingV′max=V 1+m 1 T; above that value,V max is virtually constant. The transition is sharp. This equation is consistent with a carrier model for active transport. At the transition, intracellular AIB is about 1 molecule for every 70 amino acid residues of tissue protein, vastly more than could be accommodated by AIB-binding sites in cell membranes. The transition may come from a slow process that does not fill all sites when the tissue AIB is below the transition concentration, or from an AIB-induced phase transition in the membrane.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical ecology 11 (1985), S. 953-965 
    ISSN: 1573-1561
    Schlagwort(e): Controlled release ; capillaries ; volatile substances ; pheromones ; release rates ; kinetics ; predictive model
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Controlled release formulations are required for the dissemination of behavior-modifying chemicals in insect control strategies. Among the types of formulations that have been used for some time are glass and plastic capillaries. Erratic release rates on field use of such capillaries prompted us to reexamine the release of volatile materials with regard to (1) kinetics of the release, (2) the effect of the vapor-air column above the liquid, and (3) developing a predictive model. Results indicate that the release is not zero order, and that the length of the vapor-air column is a critical factor of the system; a predictive model has been developed that will allow better design of capillary controlled-release formulations.
    Materialart: Digitale Medien
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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    Journal of atmospheric chemistry 2 (1985), S. 359-375 
    ISSN: 1573-0662
    Schlagwort(e): Photochemistry ; kinetics ; ozone decomposition ; iodine atoms ; IO radicals ; iodine oxides ; atmospheric iodine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Geologie und Paläontologie
    Notizen: Abstract The I-atom sensitised decomposition of ozone in air at 1 atm pressure and ambient temperature has been investigated. Iodine atoms were produced by photolysis of I2 using visible light or of CH3I using ultraviolet light. In both cases, the quantum yield for O3 decomposition was 1.25 (±0.11) per I atom. An important role is proposed for the self-reaction of IO radicals leading to higher oxides of iodine, IO+IO(+M)→I2O2(+M)→higher oxides, which predominated over the bimolecular reaction leading to regeneration of I atoms, IO+IO→2I+O2, with k 2a/k 2b≥4. Simple computer modelling calculations indicate that reaction (2a) may be important in determining the fate of photolabile iodine species in the atmosphere. The consequences for the behaviour of radioiodine releases are also discussed.
    Materialart: Digitale Medien
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