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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    European journal of clinical pharmacology 29 (1985), S. 221-224 
    ISSN: 1432-1041
    Keywords: fenfluramine ; norfenfluramine ; isomers ; pharmacokinetics ; healthy volunteers ; chronic treatment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The kinetics of accumulation and elimination of d- and l-fenfluramine (F) and norfenfluramine (NF) have been studied in 8 young healthy volunteers given daily doses of 60 mg of sugar-coated tablets of 20 mg dl-F hydrochloride (dl-F) t.i.d. and capsules of 15 mg d-F hydrochloride (d-F) b.i.d. for 15 days. Repeated doses of d-F plus l-F gave the same values for the parameters measured as did d-F administered alone. Steady-state concentrations of all compounds were achieved within 4–8 days. The predicted mean steady-state concentrations of d-F and elimination half-lives calculated from the results of a previous single dose study were similar to those measured at steady state in this study, confirming the lack of effect of the drug on hepatic microsomal enzymes and on kinetics after repeated dosing. d-NF concentrations were approximately half those of the parent drug and the half-life was almost twice as long. Steady state concentrations both of L-f and l-NF were consistently about 40–50% higher than of the d-isomers and there was a comparable in the half-life.
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  • 2
    Electronic Resource
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    European journal of clinical pharmacology 29 (1985), S. 331-336 
    ISSN: 1432-1041
    Keywords: nitroglycerin ; transdermal preparation ; blood viscosity ; plasma viscosity ; healthy volunteers ; haematocrit ; haemodilution
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Transdermal nitroglycerin (Nitroderm TTS 5) and a placebo were applied to 10 healthy male volunteers for 10 days. Before the first application and 6, 24, 48, 96, and 240 h thereafter, the viscosity of plasma and whole blood was measured and the packed-cell volume determined. During nitroglycerin application, the viscosity of plasma and whole blood was significantly diminished, and after 10 days it averaged 5% below the initial value. The greater the initial viscosity, the more marked was the druginduced reduction: in 5 subjects with plasma and whole-blood viscosities near the lower limit of the normal range, there was only a temporary decrease and the values reverted to their initial levels after 4 days; in the other 5 subjects, whose whole-blood viscosities were near the upper limit of the normal range, a 10% reduction was still demonstrable after 10 days. In those subjects all values measured throughout the 10-day observation period were significantly below the initial values. The haematocrit readings followed the same pattern as the alterations in viscosity. It can be assumed, therefore, that the decrease in viscosity induced by nitroglycerin results from “internal haemodilution”. The clinical relevance of the changes observed is discussed. The improvement in the rheological properties of the blood may contribute to the anti-anginal effect of Nitroderm TTS.
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  • 3
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    European journal of clinical pharmacology 28 (1985), S. 113-117 
    ISSN: 1432-1041
    Keywords: nadolol ; nifedipine ; tachycardia ; cardiovascular response ; healthy volunteers ; pharmacokinetics ; exercise heart rate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In a placebo controlled exercise protocol using healthy volunteers the effects of nadolol 80 mg and 160 mg orally and of nadolol 80 mg during treatment with nifedipine 20 mg 8 hourly were compared. Resting systolic and diastolic blood pressures were reduced by both nifedipine (p〈0.05) and nadolol (p〈0.01) acting alone. An unexpected finding was that nifedipine alone significantly inhibited exercise tachycardia (p〈0.01) (8 to 12 h post dose). Predictably both doses of nadolol produced significant reduction in exercise tachycardia which was still apparent at 24 h. There was a linear relationship between log10 plasma nadolol concentration and reduction in exercise heart rate. The combined inhibitory effects of nifedipine and nadolol 80 mg on exercise heart rate showed partial additivity but did not summate. There was no pharmacokinetic interaction between the 2 drugs. The inhibition of exercise tachycardia by nifedipine, not previously documented, is consistent with an effect of the drug on the sinus node, as has been reported in in-vitro studies, and may contribute to the drugs efficacy in angina.
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  • 4
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    European journal of clinical pharmacology 28 (1985), S. 155-158 
    ISSN: 1432-1041
    Keywords: digoxin ; digitoxin ; cardiac glycosides ; ventilation ; respiration ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Eight healthy volunteers were studied to ascertain the effect of digoxin and the relatively more lipophylic cardiac glycoside, acetyl-digitoxin on ventilation. Baseline ventilation as well as the response to the inspiration of 2.2% and 4.8% carbon dioxide were assessed. Digoxin produced a depression of minute volume and oxygen consumption whereas acetyl-digitoxin produced the opposite effect. This could be the result of a relatively greater vagomimetic effect with digoxin and a greater symphatomimetic effect with acetyl-digitoxin. These findings might have clinical implications in cardiac patients who have pulmonary disease.
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  • 5
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    European journal of clinical pharmacology 28 (1985), S. 143-148 
    ISSN: 1432-1041
    Keywords: metoprolol ; beta-adrenergic blockade ; maximal aerobic power ; acute and chronic administration ; exercise ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The acute and long-term effects of the beta1-adrenoceptor blocking agent metoprolol on blood pressure and maximal aerobic power (Wmax) were studied in 10 healthy subjects. Progressive maximal bicycle ergometer tests were performed after intravenous administration of placebo and metoprolol (0.15 mg×kg−1 and 0.30 mg×kg−1), and at the end of 4-week treatment periods with placebo, conventional metoprolol (C-M) and slow-release metoprolol (SR-M). The reduction in maximal exercise heart rate (HRmax) was correlated with the log plasma metoprolol concentration. Despite a reduction in HRmax of 23 beats/min after 0.15 mg×kg−1 metoprolol, Wmax was unaffected. After 0.30 mg×kg−1 HRmax was reduced by 40 beats/min and Wmax by 5.0%. During chronic treatment, the reductions in HRmax and Wmax were 48 beats/min and 7.5% (C-M) and 45 beats/min and 6.9% (SR-M), respectively. Resting systolic blood pressure was not changed after acute administration of metoprolol but it was reduced during chronic beta-blocker treatment. Resting diastolic blood pressure was not affected after acute or chronic treatment. Exercise systolic blood pressure remained unchanged after 0.15 mg×kg−1 metoprolol i.v. The fall in exercise systolic pressure after 0.30 mg×kg−1 metoprolol i.v. (18±5 mmHg) was significantly smaller than that during chronic treatment (30±6 mmHg C-M; 30±6 mmHg, SR-M). During chronic metoprolol treatment a certain % HRmax corresponded to a higher % Wmax than during placebo treatment, but the shift appeared to be of minor practical importance. The results show that the reduction in maximal aerobic power was comparable after acute i.v. administration and after 4 weeks oral treatment with metoprolol, if the degree of beta blockade (i.e. reduction in maximal exercise heart rate) was similar.
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  • 6
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    European journal of clinical pharmacology 28 (1985), S. 433-437 
    ISSN: 1432-1041
    Keywords: isofezolac ; probenecid ; pharmacokinetics ; anti-inflammatory drug ; drug interaction ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The interaction between isofezolac and probenecid has been studied with the aid of a specific HPLC assay for isofezolac in plasma and urine. 8 healthy adult volunteers received a single 40 mg oral dose of isofezolac before and after 3 days of loading with 0.5 g probenecid t.i.d. There was an increase in the maximum plasma isofezolac concentration from 2.44 to 3.38 µg · ml−1 when probenecid was given. The AUC of isofezolac in plasma increased from 6.73 to 11.28 µg · h · ml−1. After the last dose in a 7 day treatment with 40 mg isofezolac t.i.d., there was an increase in the maximum plasma isofezolac level from 2.84 to 4.96 µg · ml−1 when probenecid was given. The rate of absorption of isofezolac was not affected. An increase in the AUC of isofezolac in plasma was observed from 11.74 to 26.34 µg · h · ml−1. The major effect of probenecid on isofezolac metabolism was a 50% reduction in total isofezolac (free+conjugates) excreted inurine. Because of this interaction, patients given isofezolac combined with probenecid will have a higher steady-state plasma level of isofezolac than when probenecid is not administered.
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  • 7
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    European journal of clinical pharmacology 28 (1985), S. 659-664 
    ISSN: 1432-1041
    Keywords: BTS 49465 ; hypertension ; pharmacokinetics ; blood pressure effect ; heart rate effect ; side-effects ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetic and haemodynamic effects of a 200 mg oral dose of BTS 49465 (7-fluoro-1-methyl-3-methylsulphinyl-4-quinolone) were investigated in a double-blind placebo controlled study. BTS 49465 was rapidly absorbed and cleared from the systemic circulation with a half-life of 1.6 h by oxidation to the sulphone metabolite. The metabolite was cleared with a half-life of 37.6 h. Saliva concentrations of both BTS 49465 and its metabolite correlated well with the plasma concentrations. Compared to placebo, BTS 49465 produced statistically significant reductions in blood pressure and increases in heart rate both supine and after a 60° head up tilt. The time course of the haemodynamic changes suggested that the sulphone metabolite contributed to the overall hypotensive response. Plasma Renin Activity was only marginally elevated and there was no evidence of acute fluid retention. BTS 49465 was well tolerated in terms of haematological and biochemical parameters and subjective side-effects.
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  • 8
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    European journal of clinical pharmacology 28 (1985), S. 671-675 
    ISSN: 1432-1041
    Keywords: famotidine ; histamine H2-receptor antagonist ; diazepam ; hepatic elimination ; tubular secretion ; drug interaction ; cytochrome P450 ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In 8 healthy male volunteers the pharmacodynamic responses to a single dose of diazepam and a single dose of procainamide were assessed before and after pre-treatment with the H2-receptor antagonist famotidine in a randomized crossover study. The pharmacokinetics of diazepam and procainamide were also studied, and the binding of famotidine to human liver microsomes was also measured. Cimetidine induced binding changes with a spectral dissociation constant (Ks) of 0.87 mM, whereas famotidine produced no measurable spectral alteration in concentrations up to 4 mM. The elimination half-life (t1/2: 45.6 h) and total plasma clearance (CL: 0.28 ml/min/kg) of diazepam were not significantly altered by famotidine (t1/2=39.0±11.4 h; CL =0.31±0.08 ml/min/kg). Similarly, there was no enhancement of the sedative effect of diazepam by famotidine. The pharmacodynamics and pharmacokinetics of procainamide and N-acetylprocainamide (NAPA), too, were not significantly changed by famotidine: procainamide t1/2 2.9 vs 3.0 h under famotidine and renal clearance (CLR) 436 vs 443 ml/min; and NAPA CLR 195 vs 212 ml/min under famotidine. The data suggest that famotidine, in contrast to cimetidine, does not affect the pharmacokinetics of diazepam (hepatic elimination) or procainamide (tubular secretion). This new H2-receptor antagonist appears to be devoid of an interaction potential for either type of drug elimination.
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  • 9
    ISSN: 1432-1041
    Keywords: atenolol ; bopindolol ; metoprolol ; oxidation polymorphism ; debrisoquine ; bufuralol ; stereoselective metabolism ; pharmacological effect ; healthy volunteers ; beta-blocker
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Ten healthy subjects whose genetic oxidative phenotype had been determined (6 extensive and 4 poor metabolizers of the debrisoquine-sparteine type of polymorphism) received single oral doses of 3 beta-blockers: atenolol, bopindolol and metoprolol. The plasma concentrations and the extent of the decrease in exercise-induced tachycardia were determined. The oxidative polymorphism was only significant for substances that had a high hepatic first pass metabolism, such as metoprolol. The metabolic pathway under genetic control was highly stereoselective. This observation must be taken into account when assessing the relation between the plasma concentration and effect of these drugs, which are often administered as racemic mixtures.
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  • 10
    ISSN: 1432-1041
    Keywords: converting enzyme inhibitor ; CGS 14824A ; pharmacodynamics ; plasma renin ; plasma angiotensin ; aldosterone ; side-effects ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The converting enzyme inhibitor CGS 14824A was evaluated in 15 healthy male volunteers. First, the efficacy of a single 5 or 10 mg oral dose in antagonizing the pressor response to exogenous angiotensin I was tested in 2 subjects. Blood pressure and heart rate were monitored continuously through an intra-arterial catheter. CGS 14824A 5 mg reduced the response to angiotensin I within 75 min to 50%, and 10 mg within 1 h to less than 25%, and for a period of more than 4 h. Subsequently, plasma renin and converting enzyme activity, plasma angiotensin I, angiotensin II and aldosterone were measured serially before and up to 72 h following oral administration of 2, 5, 10 or 20 mg CGS 14824A to groups of 5 volunteers. Plasma converting enzyme activity fell to well below 10% of baseline within 1 h after administration of 5 mg or more CGS 14824 A. Within 2 h following 2 mg p.o., a similarly low level was reached. Twenty four hours following the 20 mg dose, plasma converting enzyme activity was still below 10%. As expected, plasma renin activity and angiotensin I rose while angiotensin II and aldosterone fell following the 2 mg dose. This pattern of effects was enhanced by increasing the dose. Nonetheless, 24 h after the 20 mg dose, plasma angiotensin II and aldosterone had returned to their baseline levels. No side-effects occurred. Thus, in normal volunteers, CGS 14824A was an effective, potent and long acting converting enzyme inhibitor.
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  • 11
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    European journal of clinical pharmacology 28 (1985), S. 273-277 
    ISSN: 1432-1041
    Keywords: ketanserin ; catecholamines ; renin activity ; norepinephrine ; epinephrine ; dopamine ; healthy volunteers ; plasma levels
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary In a placebo controlled, single blind, randomized cross over study catecholamines (CA) and renin activity (PRA) in plasma were measured in 2 female and 4 male healthy volunteers, at rest in the supine position, following a single intravenous injection of 0.15 mg/kg ketanserin (K) and placebo (P, 10 ml saline). K caused a significant increase in the area under the plasma norepinephrine (NE) time curve (AUCNE) from 13,200 to 18,100 ng × 1−1 × min for 1 hour after the injection. The area under the plasma epinephrine (E) time curve (AUCE) was also increased but to a lesser extent; it was significantly elevated from 54 to 68 ng × 1−1 × min for 1 minute after the injection. Dopamine (DA) and PRA did not show any significant response to ketanserin. Following the P injection, none of the four parameters showed any significant change.
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  • 12
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    European journal of clinical pharmacology 28 (1985), S. 229-230 
    ISSN: 1432-1041
    Keywords: diazepam ; dipotassiumchlorazepate ; benzodiazepines ; bioavailability ; administration ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Dipotassium chlorazepate (DPC) and diazepam (DZM) were given i.m. and i.v. to 6 healthy volunteers in doses of 20 mg (48.9 µmol) DPC and 15 mg (52.0 µmol) DZM. The interval between the injections was at least 1 week. Plasma samples were analyzed for DPC and DZM by HPLC. The bioavailability of DPC and DZM after i.m. administration, determined from computer calculated AUCs, was 1.04 and 0.85, respectively.
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  • 13
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    European journal of clinical pharmacology 28 (1985), S. 463-467 
    ISSN: 1432-1041
    Keywords: ceftizoxime ; cephalosporins ; renal excretion ; tubular reabsorption ; tubular secretion ; healthy volunteers ; biliary excretion ; clearance studies
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The kinetics of ceftizoxime, a newly developed cephalosporin, were evaluated in 6 healthy subjects, with respect to its excretory pathways especially by the biliary route. Total, renal and biliary clearance were determined at two different steady states. Steady state was achieved by constant intravenous infusion (604.1 mg/h) over 6 h after an initial loading dose (750 mg); 1.5 h after discontinuation of that infusion, a further infusion was commenced at a lower rate (284 mg/h) over 3 h, the second steady state being reached 0.5 to 1.0 h later. The drug was mainly excreted by the kidneys (56.7 to 92.9% of the dose). Biliary excretion, measured by the duodenal perfusion and marker dilution technique, was low (0.2 to 7.8% of the dose). Urinary and biliary excretion as well as total clearance were not dose-dependent. However, there was pronounced interindividual variation in total (35.2 to 236 ml/min) and renal clearance (10.6 to 208 ml/min), which could both be explained by varying interindividual urinary flow rates (mean flow rate: 0.99 ml/min to 3.14 ml/min). Intraindividual variation in renal clearance was less pronounced, but in the same subject changes in renal clearance were correlated with changes in urinary flow rate. From the varying renal clearance, which exceeded the glomerular filtration rate at high urinary flow rates and was below it at low urinary flow rates, it can be concluded that, in addition to glomerular filtration, tubular secretion and tubular reabsorption are involved in the renal excretion of ceftizoxime. The half-life calculated from two point estimates after discontinuation of the infusion at the higher rate tended to be longer in subjects with high total clearance (e. g. 1.4 h, clearance 223 ml/min) and shorter in subjects with low total clearance (e.g. 0.85 h, clearance 35.2 ml/min). From this it is concluded that the true half-life was not observed after discontinuation of the infusion.
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  • 14
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    European journal of clinical pharmacology 28 (1985), S. 607-609 
    ISSN: 1432-1041
    Keywords: growth hormone ; valproate ; GABA ; stress ; exercise ; healthy volunteers ; GABAergic transmission
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effect of the GABAergic drug sodium valproate (SV) on the exercise-induced release of growth hormone (GH) was investigated in 10 healthy males. The exercise test consisted of using a stationary bicycle ergometer at 450 kg/min for 20 min. SV 600 mg blunted the increase in GH induced by the exercise, suggesting GABAergic regulation of GH secretion in man, at least under certain physiological conditions.
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  • 15
    ISSN: 1432-1041
    Keywords: moclobemide ; Ro 11-1163 ; pharmacokinetics ; bioavailability ; MAO activity in platelets ; monoamine metabolites in urine ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The plasma concentrations of the MAO-inhibitor moclobemide (Ro 11-1163) were determined in six healthy male subjects after oral (tablets) administration. Effects on MAO activity in platelets and excretion of monoamine metabolites in urine were investigated. The design of the study was a double-blind cross-over study with single oral doses of placebo, 50, 100 and 200 mg of moclobemide. The elimination profile of the drug showed that the half life of the unchanged drug ranged between 1 and 2 h except in one subject with a half-life of about 4 h. The mean bioavailability calculated using flow model concepts was F=0.43 after 50 mg, F=0.47 after 100 mg and F=0.59 after 200 mg. The outlier with a t1/2 of 4 h was found to have a bioavailability of more than 0.80 after all 3 doses. The slightly increasing bioavailability with higher doses was interpreted as evidence of saturable hepatic first-pass elimination of the drug. MAO activity in platelets was measured before and 2, 6 and 24 h after drug administration. No inhibition of platelet MAO was obtained at any point in time or dose level, as to be expected since moclobemide preferentially inhibits MAO A. Urine excretion of the monoamine metabolites homovanillic acid (HVA), dihydroxyphenylacetic acid (DOPAC), 3-methoxy-4-hydroxy-phenylglycol (MOPEG) and 5-hydroxyindoleacetic acid (5-HIAA) was followed during 48 h after placebo, 50 and 200 mg of moclobemide. Time but not dose contributed significantly to the variability in excretion of the monoamine metabolites. An apparent reduction of HVA and DOPAC levels was obtained in the early phase after the administration of 200 mg of moclobemide. In 1 subject with a mild drug reaction a pronounced decrease in the levels of all the metabolites was obtained. In the other 5 subjects, the compound was very well tolerated with a few reported side-effects like increased activity, somnolence or sweatings. There was a slight but significant increase in blood pressure following 50 and 100 mg but not 200 mg of moclobemide.
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  • 16
    ISSN: 1432-1041
    Keywords: sulphinpyrazone ; metabolism ; single dose ; chronic treatment ; pharmacokinetics ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of sulphinpyrazone and its major metabolites (sulfide, sulfone, p-hydroxysulfone and p-hydroxy-sulphinpyrazone) were investigated in 9 volunteers after a single oral dose as well as after chronic treatment for 23 days. Chronic administration of sulphinpyrazone, in comparison with a single oral dose, led to significant changes in plasma AUC (115.86 to 42.90 mg/l·h), in renal clearance (1.06 to 1.80l/h), in hepatic intrinsic clearance (319.0 to 598.0l/h), and in the unbound fraction in plasma 1.15 to 1.69%) and in tissue (2.73 to 1.31%). The volume of distribution changed from 20.24 to 52.041. The steady state concentrations predicted from the single dose were significantly higher than the values found after chronic treatment. The results suggest that sulphinpyrazone induces its own metabolism. The metabolism of the sulfone, p-hydroxysulfone and the p-hydroxy-sulphinpyrazone to further degradation products was also induced. Chronic treatment with sulphinpyrazone reduced the plasma AUC of the sulfide and caused a decrease in its elimination half-life (20.9 to 14.3 h). Since considerable amounts of the sulfide are formed in the G.I. tract, it is suggested that besides the induction of metabolism, bacteria which reduce sulphinpyrazone to the sulfide may also be responsible for the observed pharmacokinetic changes.
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  • 17
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    European journal of clinical pharmacology 29 (1985), S. 67-71 
    ISSN: 1432-1041
    Keywords: dipyrone ; dipyrone metabolites ; human protein binding ; analgesic antipyretic drugs ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Four metabolites of dipyrone, 4-methyl-aminoantipyrine (MAA), 4-aminoantipyrine (AA), 4-formylaminoantipyrine (FAA) and 4-acetylamino-antipyrine (AAA) can be identified in human plasma after its oral administration. The plasma protein binding of the metabolites in samples from 20 healthy volunteers was determined by ultrafiltration. None of the metabolites were found to be extensively bound to plasma proteins. The binding of MAA and AA was relatively higher than of FAA and AAA, as expected from their chemical structure. The mean percentage plasma protein binding was 57.6% for MAA, 47.9 for AA, 17.8 for FAA and 14.2% for AAA. The correlation between the unbound concentration in plasma and the total concentrations of MAA, AA, FAA and AAA was linear. No association was evident between the total protein plasma concentration and the extent of binding. The possible therapeutic implications related to protein binding of several analgesic and non-steroidal anti-inflammatory drugs are discussed.
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  • 18
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    European journal of clinical pharmacology 29 (1985), S. 91-95 
    ISSN: 1432-1041
    Keywords: midazolam ; 1-hydroxymethylmidazolam ; pharmacokinetics ; dose proportionality ; benzodiazepine ; healthy volunteers ; side-effects
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetics of midazolam and 1-hydroxymethylmidazolam were investigated following oral administration of 7.5, 15 and 30 mg doses of midazolam in solution to 12 healthy subjects. Compared to the 7.5 mg dose, the Cmax and AUC parameters of both midazolam and 1-hydroxymethylmidazolam increased proportionally after the 15 mg dose and more than proportionally after the 30 mg dose. The t1/2 for midazolam remained relatively constant between the 7.5 and 15 mg doses whereas it increased slightly but significantly after the 30 mg dose. These data indicated that the pharmacokinetics of midazolam and 1-hydroxymethylmidazolam were linear between the 7.5 and 15 mg oral dose range. However, after the 30 mg dose, the systemic availability of midazolam and the AUC for 1-hydroxymethylmidazolam appeared to be greater than that anticipated from the lower doses, possibly due to saturation of midazolam first-pass metabolism. This ist not expected to have any clinical significance under the conditions of therapeutic use.
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  • 19
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    European journal of clinical pharmacology 29 (1985), S. 413-416 
    ISSN: 1432-1041
    Keywords: nifedipine ; indomethacin ; whole blood aggregometry ; 6-keto-prostaglandin F1α ; blood pressure ; platelet aggregation ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Pre-incubation of human platelets with nifedipine in vitro or treatment of normal volunteers with nifedipine, 30 mg daily for one week, did not alter ADP induced aggregation measured by whole blood aggregometry. 6-oxo-Prostaglandin F1α remained undetectable in plasma following oral administration of nifedipine to normal volunteers. The hypotensive response to intravenous nifedipine administration was similar in spontaneously hypertensive rats pretreated with indomethacin or placebo. These results conflict with previous reports that nifedipine alters platelet aggregation and prostaglandin metabolism.
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  • 20
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    European journal of clinical pharmacology 28 (1985), S. 221-222 
    ISSN: 1432-1041
    Keywords: calcium entry blockers ; bronchomotor tone ; ethanol ; nifedipine ; flunarizine ; diltiazem ; verapamil ; healthy volunteers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The effect of various Calcium Entry Blockers (CEBs; nifedipine, flunarizine, diltiazem, verapamil) on ethanol-induced bronchoconstriction was studied in normal healthy volunteers. Nifedipine and diltiazem inhibited the bronchoconstriction and verapamil and flunarizine had no effect. The data favour the general hypothesis of differential tissue sensitivity to the various CEBs. The activity of CEBs on bronchomotor tone may be of therapeutic value in patients in whom bronchodilator activity is recommended in addition to the cardiovascular action.
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  • 21
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    European journal of clinical pharmacology 28 (1985), S. 411-417 
    ISSN: 1432-1041
    Keywords: ketanserin ; ketanserinol ; pharmacokinetics ; age ; healthy volunteers ; bioavailability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The bioavailability of ketanserin has been examined in a cross-over experiment in 21 elderly subjects (aged 59–72 years) by administration of tablets (40 mg), solution (40 mg) and injectable solution (10 mg). After two weeks of treatment with 40 mg ketanserin tablets further 18 blood samples for analysis were collected under steady-state conditions. Plasma levels were measured by HPLC. The absolute bioavailability of ketanserin tablets was 52.7%; their relative bioavailability compared to a solution containing an equal quantity of active compound was 85.5%. Therefore, the low absolute bioavailability of ketanserin cannot be attributed to the formulation. The active compound was rapidly liberated from the tablet, reaching a peak of 103.8 ng/ml after 0.97 h. Individual plasma level-time curves were fitted to an open three compartment model and a half-life of 17.7±7.26 h was calculated for the terminal elimination phase. An average terminal elimination half-life of 15.4±4.2 ng/ml was found after administration of the ketanserin solution. Multiple dosing with 40 mg tablets b.d.s. resulted in an AUC over one dosing interval at steady-state of 666±201 ng × h/ml. The AUC extrapolated to infinity was 1200±405 ng × h/ml for the last tablet. This is 1.8-times the AUC in one dosing interval, and 2.3-times the AUC of a single dose. Under steady-state conditions, the mean peak plasma level was 155.1 ng/ml (1.08 h after dosing) and the terminal half-life was 19.1±5.1 h. For the metabolite ketanserinol terminal half-lives of 21.4 h after a single tablet and 31.0 h after discontinuation of multiple dosing were calculated. Compared to the parent compound there was much more marked accumulation of ketanserinol. Despite moderate accumulation and prolongation of the terminal half-life of ketanserin under steady-state conditions, dosage adjustment is not required in elderly people. First-pass metabolism and bioavailability remained in the range found in previous studies of ketanserin in young subjects.
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  • 22
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    European journal of clinical pharmacology 28 (1985), S. 567-571 
    ISSN: 1432-1041
    Keywords: vinpocetine ; cognitive function ; information processing ; memory ; healthy volunteers
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Twelve healthy female volunteers received pre-treatments with vinpocetine 10, 20, 40 mg and placebo (t.d.s.) for two days according to a randomised, double-blind crossover design. On the third day of treatment and 1 h following morning dosage, subjects completed a battery of psychological tests including Ciritcal Flicker Fusion (CFF), Choice Reaction Time (CRT), Subjective Ratings of Drug Effects (LARS) and a Sternberg Memory Scanning Test. No statistically significant changes from placebo were observed on CFF, CRT or subjective ratings of drug effects. However, memory as assessed using the Sternberg technique was found to be significantly improved following treatment with vinpocetine 40 mg when compared to placebo and results suggested a localised effect of the drug on the serial comparison stage of the reaction process.
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  • 23
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    European journal of clinical pharmacology 28 (1985), S. 631-636 
    ISSN: 1432-1041
    Keywords: salbutamol ; histamine plasma concentration ; bronchorelaxation ; healthy volunteers ; induced bronchoconstriction ; carbachol ; bronchoconstrictor mediators
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary Plasma histamine in 8 normal subjects was measured before and after inhalation of carbachol to induce a 50% fall in specific airway conductance (SGaw). The measurements were repeated 5 min after inhalation of salbutamol or placebo. No significant change in plasma histamine occurred after placebo or carbachol inhalation, despite the persistent induced bronchospasm after the latter treatment. In contrast, plasma histamine was significantly increased from 0.25 to 0.43 ng/ml after salbutamol inhalation. Simultaneously, induced bronchospasm was relieved, from 51% to 103% of baseline SGaw. Thus, the relief of carbachol-induced bronchospasm by salbutamol was associated with a rise in plasma histamine. Since salbutamol itself is a potent inhibitor of mast cell degranulation and histamine release, the present findings suggest that histamine may be released and sequestered within the lungs during carbachol-induced-bronchospasm, and also that desequestration of bronchoconstrictor mediators accumulated at the point of contact of bronchial smooth muscle may contribute to the relief of bronchospasm by salbutamol.
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  • 24
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    European journal of clinical pharmacology 28 (1985), S. 649-652 
    ISSN: 1432-1041
    Keywords: digitoxigenin ; monodigitoxoside ; bisdigitoxoside ; biovailability ; healthy volunteers
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary The pharmacokinetic behavior of digitoxigenin is affected by the number of glycosides present. This study was conducted to compare the bioavailabilities of the bis- and monodigitoxosides of digitoxigenin in man. Intravenous and oral doses of the two drugs were administered to six normal volunteers. Blood samples were collected up to 28 days after each dose, and assayed for the specific drug administered and for total radioassayable drug. Both drugs were virtually completely absorbed, based on serum concentrations of administered drug plus metabolites. However, the mean bioavailability of unchanged bisdigitoxoside was only 56.3% indicating that substantial metabolism occurred prior to entry into the systemic circulation. Monodigitoxoside was virtually completely metabolized prior to entry into the systemic circulation.
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  • 25
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    European journal of clinical pharmacology 28 (1985), S. 685-688 
    ISSN: 1432-1041
    Keywords: prostaglandin analogue ; renal function ; vasodilator ; L-644,122 ; healthy volunteers
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    Topics: Chemistry and Pharmacology , Medicine
    Notes: Summary L-644,122 is a chemically stable vasodilator prostaglandin analogue. It is a selective renal vasodilator in dogs. The object of the present study was to determine whether it increases effective renal plasma flow (ERPF) in man. L-644,122 was administered intravenously to 4 healthy volunteers and by mouth to 4 mild hypertensives. It did not increase ERPF. Instead it acted as a non-specific vasodilator, lowering diastolic blood pressure and increasing heart rate. An unexpected increase in glomerular filtration rate (19% greater than placebo) after low dose intravenous L-644,122 merits further study.
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  • 26
    ISSN: 1573-1561
    Keywords: Chiral semiochemicals ; pheromones ; enantiomeric composition ; Ips pini ; Coleoptera ; Scolytidae ; Apis mellifera ; Hymenoptera ; apidae ; Cryptolestes Ferrugineus ; Cucujidae ; acetyl lactate diastereoisomers
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A method is described for determining the enantiomeric composition of chiral alcohols, lactones, and hydroxy acids in quantities ranging from 25 ng to 10 μg. Derivatization of the substance with chirally pure acetyl lactate, followed by splitless capillary gas chromatography, enables enantiomeric determinations to be made within 1–3% of the actual value. This technique was applied in the determination of semiochemical inIps pini (Say),Apis mellifera (L.), andCryptolestes ferrugineus (Stephens). The results indicate that considerable variability exists within populations of some insects in the composition of their chiral semiochemicals, whereas others produce substances of constant composition.
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  • 27
    ISSN: 1573-1561
    Keywords: Isoflavonoids ; structure-activity relationships ; insect feeding-deterrent activity ; Costelytra zealandica ; Coleoptera ; Scarabaeidae ; stereochemistry
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A number of naturally occurring isoflavonoids of differing substitution patterns and oxidation states have been tested for feeding deterrent activity in a bioassay with larvae ofCostelytra zealandica White. The most active deterrents, which reduced feeding significantly at 0.2-1.0 μg/g, are those compounds containing a ring B-fused cycloprenoid moiety. The least active compounds were highly oxidized coumestans and isoflavones. The ring B-fused cyclic isoprenoid moiety and the presence of a 2'-oxy function appear to be structural features important for high activity. It is suggested that the feeding deterrent activity of isoflavonoids relates to their stereochemistry and that the most active compounds have or can adopt a similar nonplanar molecular shape with a similar arrangement of polar and lipophilic groups.
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  • 28
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed-phase ; Codeine phosphate drug substance ; Opium alkaloids
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    Topics: Chemistry and Pharmacology
    Notes: Summary A rapid procedure for the evaluation of codeine phosphate drug substance derived from poppy straw or opium concentrate is described. The gradient HPLC procedure employs a pH 2.5 phosphate buffer, methanol and acetonitrile mobile phase at 40°C and a μBondapak C-18 column. Eight opium alkaloids, including the four major alkaloids, are separated from each other. The paper describes details of the assay procedure and presents data documenting the linearity, specificity, precision, and sensitivity of the method.
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  • 29
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; External variance determinations ; Column and system compatibility ; Microbore and fast LC
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    Topics: Chemistry and Pharmacology
    Notes: Summary The demand for faster, more economic and convenient high-efficiency LC analyses has led to the development of microbore and fast columns. However, to utilize their benefits, the low column dispersions produced by these new technologies necessitate low external variances in the total system. This paper describes the determination of the external variance of microbore, fast and conventional LC systems by a column method. Compatibility with the relevant column technologies is evaluated by a method involving the comparison of the external and column dispersions. Direct comparison of chromatograms of an 8-component mixture, on a set of columns of various diameters and lengths, shows the relative speed, economy and sensitivity obtainable in practice. The problem of reduced sample loadability is considered and the practical solution of peak compression illustrated.
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  • 30
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Retention prediction system ; UV multichannel detector ; Polycyclic aromatic hydrocarbons
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    Topics: Chemistry and Pharmacology
    Notes: Summary The retention prediction system assisted by a micro-computer coupled with an UV multichannel detector has been investigated in the separation of polycyclic aromatic hydrocarbons. The method offered very precise identification of components in NBS-SRM-1647 sample without any standard reference substances. It has been proven that the system makes very precise, non-pollutive and convenient environmental analysis possible.
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  • 31
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    Chromatographia 20 (1985), S. 313-322 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Tetracyclines antibiotics ; Quantitation
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    Topics: Chemistry and Pharmacology
    Notes: Summary The use of high-performance liquid chromatography (HPLC) for the identification and determination of tetracycline antibiotics is reviewed. HPLC chromatograms provide fast identification by retention time, tR, and precise quantitation by measurement of peak height or peak area. For separation of tetracycline compounds, most HPLC methods use reversed-phase C18 or C8 columns and UV detection. The HPLC solvent system should have a pH of about 6 to prevent steric changes in the tetracycline molecule. For accurate quantitation it is necessary to avoid tailing and this is accomplished by adding a zwitter ion to the solvent system. Methanol and acetonitrile are frequently used as organic modifiers in these solvent systems. In a single analysis, HPLC methods can be used to separate as many as nine or ten commercially used tetracycline compounds and to determine four to five tetracyclines in commercial tetracycline preparations or in biological fluids.
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  • 32
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Resolution of optical isomers ; Chiral column ; Pyrethroids ; Fenvalerate
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    Topics: Chemistry and Pharmacology
    Notes: Summary The separation of the optical isomers of fenvalerate [cyano(3-phenoxyphenyl)methyl 2-(4-chlorophenyl)-3-methylbutyrate] has been carried out by high-performance liquid chromatography (HPLC) on a chiral column with (R)-N-3,5-dinitrobenzoyl-phenyl-glycine (DNBPG) covalently bonded on aminopropyl silica and eluted with mixtures of methanol, 2-propanol, and hexane. The system was applied to the analysis of Pydrin®, an emulsifiable concentrate formulation of fenvalerate, and to the residue analysis of fenvalerate in milk samples. For the analysis of Pydrin® the only requirement was the proper dilution of Pydrin® with hexane. For the analysis of residues in milk, fenvalerate was extracted with hexane after precipitating the milk proteins with acetonitrile and removing the precipitate by filtration; the hexane extract was concentrated to small volume and filtered before being analyzed by HPLC.
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  • 33
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    Chromatographia 20 (1985), S. 487-494 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Size-exclusion chromatography ; Controlled-porosity glasses ; Boron-enriched glass surface ; Adsorptive properties
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    Topics: Chemistry and Pharmacology
    Notes: Summary Controlled-porosity glasses (CPG) are sieves for macromoleculars, very widely applied in chromatographic columns for the separation of polymers and biopolymers by means of size-exclusion chromatography (SEC) and affinity chromatography. This paper deals with the influence of the thermal treatment of CPG on the elution of polymers in SEC columns. The problem is examined for a few mobile phases and for glasses having different porosities. Additionally, the SEC results obtained are compared with the adsorption properties of the glases investigated.
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  • 34
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    Journal of chemical ecology 11 (1985), S. 11-20 
    ISSN: 1573-1561
    Keywords: European elm bark beetle ; Scolytus multistriatus ; Coleoptera ; Scolytidae ; control ; chlorpyrifos ; cacodylic acid ; trapping ; trap tree ; Dutch elm disease ; multilure ; attraction
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract European elm bark beetles,Scolytus multistriatus (Marsh.), were strongly attracted to American elms,Ulmus americana L., baited with theS. multistriatus attractant, multilure, or killed by injection of the arboricide, cacodylic acid; a combination of the two treatments was most attractive. Comparisons of beetle catches on sticky bands affixed to the trees with samples of bark from the same trees showed that the number of beetles landing on cacodylic acid-treated trees was approximately 40 times greater than the number boring into them. Spraying the bark with the insecticide chlorpyrifos had no direct effect on attraction. No live bark beetle brood was found in trees that had been treated with cacodylic acid or chlorpyrifos, but trees that were only baited or left untreated (check) were attacked, killed, and colonized. We suggest that the contribution of the cacodylic acid trap tree technique to Dutch elm disease control will be enhanced by baiting treated trees with multilure and spraying their lower boles with 0.5% chlorpyrifos. This treatment will eliminate diseased and unwanted elms as potential breeding material and kill large numbers of elm bark beetles that might otherwise innoculate healthy elms with the Dutch elm disease fungus.
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  • 35
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    Journal of chemical ecology 11 (1985), S. 311-318 
    ISSN: 1573-1561
    Keywords: cucurbitacins ; defense compounds ; Diabrotica spp. ; Acalymma vittatum ; insect/plant interaction ; Tenodera aridifolia sinensis ; Coleoptera ; Chrysomelidae ; Orthoptera ; Mantidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Four species of diabroticites with different host specificities are shown for the first time to sequester cucurbitacins. While all beetles fed on an artificial diet (no cucurbitacins) were readily consumed by Chinese praying mantids, a significant proportion of adultDiabrotica balteata (72%),D. undecimpunctata howardi (46%), andD. virgifera virgifera (24%) fed on squash fruit containing cucurbitacins B and D were rejected. Moreover, even when adults did not feed on cucurbitacins, 21–24% ofAcalymma vittatum were rejected by the mantids which is consistent with larval sequestration of cucurbitacins. The mantids failed to learn to avoid any of the beetle species despite adverse effects associated with ingestion, i.e., uncoordination, regurgitation, etc. A cucurbitacin D metabolite accumulated and was sequestered for extended periods of time in the hemolymph of all four species. In addition, female beetles that had ingested cucurbitacins laid eggs containing substantial amounts of cucurbitacins.
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  • 36
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    Journal of chemical ecology 11 (1985), S. 1083-1092 
    ISSN: 1573-1561
    Keywords: Chemical defense ; Zophobas atratus ; Coleoptera ; Tenebrionidae ; defensive secretion ; gland recharge ; defensive quinone ; quinone production
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Beetles were milked of their abdominal defensive secretion at three different frequencies over the first 36 days of adult life. Secretion production decreased greatly with age from a maximum of 94 nmol/day at 4–6 days to a basal level of about 25 nmol/day at 30–40 days. Ethyl- and methylquinone comprised the bulk of the secretion and were most strongly affected by age. Benzoquinone was most strongly affected by milking frequency. An average adult produced an estimated 4445 nmol of total secretion in its 5-month life-span but had reservoirs large enough to store 11,000 nmol. Males produced more secretion than females because of their larger size and inherent sexual differences. As they aged, mated females showed a more rapid decrease in production that virgin females. The defensive system appears to be programed to charge glands rapidly with secretion early in adult life and fall of to a low recharge rate little affected by discharge.
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  • 37
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    Journal of chemical ecology 11 (1985), S. 73-83 
    ISSN: 1573-1561
    Keywords: Colorado potato beetle ; Leptinotarsa decemlineata ; Coleoptera ; Chrysomelidae ; feeding deterrents ; Solanaceae ; Solanum alkaloids ; chemo-receptors ; mouthpart sensilla ; tomatine ; solanine ; chaconine ; demissine ; leptine III
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Steroidal glycoalkaloids, found in species of the Solanaceae, elicit bursting activity in galeal and tarsal chemosensilla of adult Colorado potato beetles. The effect has an average latency of 6–12 sec, depending on the sensillum/alkaloid combination. A 20-sec alkaloid treatment is often suffficient to render galeal sensilla unresponsive to gamma-aminobutyric acid, normally an effective stimulant. The alkaloids have similar effects on galeal sensilla of larval Colorado potato beetles and on labellar chemosensilla of the blowfly. It is concluded that these compounds act independently of any specialized chemoreceptor in the Colorado potato beetle, and that association of the Colorado potato beetle with solanaceous plants has not led to evolution of a specific receptor forSolanum glycoalkaloids.
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  • 38
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    Journal of chemical ecology 11 (1985), S. 1371-1387 
    ISSN: 1573-1561
    Keywords: Asymmetric synthesis ; stereoisomers ; sex pheromone ; Diabrotica ; Coleoptera ; Chrysomelidae ; (R)-2-methylbutyric acid ; HPLC ; diastereomers
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Details of the syntheses of the four stereoisomers of 8-methyl-2-decanol and its propanoate ester are given. The racemic ester, two of its stereoisomers, and one stereoisomer as an acetate are attractive to several species ofDiabrotica. The key steps in the syntheses involve high-performance liquid chromatograpic resolutions of diastereomers to achieve high configurational enrichment of each site and generation of (R)-2-methylbutyric acid by chemical degradation ofd-isoleucine.
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  • 39
    ISSN: 1573-1561
    Keywords: Benzoquinones ; defensive secretion ; 2-heptadecanone ; hepta-dec-10-en-2-one ; heptadecene ; 2-methoxyphenol ; nonadec-lO-en-2-one ; 2-pentadecanone ; pentadecene ; 2-pentanone ; Uloma tenebrionoides ; Coleoptera ; Tenebrionidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The defensive secretion ofUloma tenebrionoides (White, 1846) contains benzoquinone, 2-methylbenzoquinone (toluquinone), and 2-ethylben-zoquinone as in other tenebrionids, together with 2-methoxyphenol, pentadecene, heptadecene, 2-pentanone, 2-pentadecanone, 2-heptadecanone, heptadec-10-en-2-one and (Z)-nonadec-10-en-2-one. The latter four methyl ketones have not previously been identified in tenebrionid beetles, and the unsaturated ketones are novel arthropod chemicals.
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  • 40
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    Journal of chemical ecology 11 (1985), S. 1553-1565 
    ISSN: 1573-1561
    Keywords: Herbivory ; chemical quantitative variation ; specialist herbivore ; parasitism ; growth reduction ; Encelia farinosa ; Asteraceae ; Trirhabda geminata ; Coleoptera ; Chrysomelidae ; Chaetonodexodes vanderwulpi ; Diptera ; Tachinidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Larvae of the monophagous herbivore,Trirhabda geminata, selectively eat particular plants and plant parts of its natural host,Encelia farinosa. Measurements of leaf damage and larval positions on branches through time support this observation. Time-lapse movie photography revealed that larvae are sufficiently mobile to search most of a plant in a 48-hr period and that aggregations were the result of larval activity and not directly the result of oviposition. Experiments withT. geminata larvae on artificial diets containing a range of natural concentrations of chemical extracts fromE. farinosa leaves showed that the larvae grew significantly slower and had a lower overall survivorship at the high concentration. Combining the results of all choice tests, larvae appeared unable to distinguish between high- and low-concentration agar diets. Considered individually, larval preferences for natural production concentrations changed as the season progressed. Early-season larvae preferred low-concentration leaves, while late-season larvae preferred high-concentrations. Measurements of chemical and nitrogen content of leaves selected by larvae in the field confirmed this pattern. Percent parasitism in field-collected larvae increased with season as the larval population decreased. This combination of slowed growth and increasing parasitism and predation is a putative defense strategy ofEncelia farinosa to prevent adaptation by a specialist herbivore to the total range of compounds elaborated.
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  • 41
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    Journal of chemical ecology 11 (1985), S. 539-544 
    ISSN: 1573-1561
    Keywords: Ammonia utilization ; l-canavanine catabolism ; Caryedes brasiliensis ; Coleoptera ; Bruchidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The seed predator,Caryedes brasiliensis [Bruchidae] generates appreciable ammonia in its dietary use and detoxification ofl-canavanine and its catabolic product,l-canaline.l-Canavanine is a toxic allelochemical ofDioclea megacarpa seeds, the food of the developing larvae. Bruchid beetle larvae rely upon glutamic acid dehydrogenase and glutamine synthetase to use ammonia for glutamic acid synthesis from 2-oxoglutaric acid and conversion of the former to glutamine. These reactions provide the larvae with a means for metabolically eliminating ammonia. Proline serves as a carbon skeleton source for glutamic acid formation.
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  • 42
    ISSN: 1573-1561
    Keywords: Oryzaephilus surinamensis ; saw-toothed grain beetle ; Coleoptera ; Silvanidae ; attractant ; carobs ; Ceratonia siliqua ; volatiles ; vacuum distillation ; hexanoic (caproic) acid
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Vacuum distillation of heat-treated carobs gave an aqueous, colorless, sweet-smelling distillate which was tested over a wide range of concentrations and found to be highly attractive to adultOryzaephilus surinamensis (L.). The materials responsible for the aroma were isolated from the distillate by saturating with sodium chloride and extracting into diethyl ether as separate acidic, neutral, and basic fractions. The extraction efficiency was checked by recombining portions of the three fractions and replacing the diethyl ether with water to give a “reconstituted distillate;” this was almost as attractive as the original distillate. Bioassay of aqueous solutions of the three separate fractions showed that the acidic was attractive, while the neutral and basic had little effect. The five major components of the acidic fraction were found to be acetic, isobutyric,n-butyric, 2-methylbutyric, and hexanoic (caproic) acids. Bioassay of these in aqueous solution, both separately and combined, showed that hexanoic acid was the most attractive and may be responsible for both the longer-lasting attractive effect of the carob distillate and for the effectiveness of carobs themselves used in bait bags to detect stored product insects.
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  • 43
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    Journal of chemical ecology 11 (1985), S. 767-779 
    ISSN: 1573-1561
    Keywords: Host plant ; biological control of weeds ; Trirhabda bacharides ; Coleoptera ; Chrysomelidae ; Compositae ; Baccharis ; green leaf volatiles ; plant odor ; electroantennogram ; olfaction
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Electroantennograms (EAGs) were recorded fromTrirhabda bacharides Le Conte (Coleoptera: Chrysomelidae) females to 28 odorants and volatiles emanating from leaves of 26 plant species including three known host plants,Baccharis halimifolia L.,B. neglecta Britt, andB. salicina T. & G. (Compositae: Asterae). Antennal receptors were highly responsive to components of the green leaf volatile complex, especially 6-carbon saturated and monounsaturated alcohols andtrans-2-hexenal. EAGs elicited by heptanal were greater than those elicited by any other saturated aldehyde. Oxygenated monoterpenes were more active than monoterpene hydrocarbons. β-Bisabolol was the most active sesquiterpene. In general, EAGs to volatiles emanating fromBaccharis and other composite species were greater than those elicited by species from other families. Furthermore, when one considers only plants occurring in the environs ofT bacharides hostB. neglecta, EAGs elicited by its host plant were at least two times greater than those elicited by other coinhabiting plants.
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  • 44
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    Journal of chemical ecology 11 (1985), S. 999-1007 
    ISSN: 1573-1561
    Keywords: Pine engraver beetle ; Ips pini ; Coleoptera ; Scolytidae ; (+)-ipsdienol ; (−)-ipsdienol ; pheromone receptor ; response specificity ; electrophysiology ; interpopulational hybrid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Electrophysiological studies of pheromone receptor cells keyed to ispdienol were performed in laboratory-raised hybrids of the eastern and western populations of the pine engraver,Ips pini. As previously shown in the parental beetles, the receptor cells keyed to ipsdienol could be classified as two distinct types: one keyed to (+)- and one to (−)-ipsdienol. None of the 20 ipsdienol cells recorded from F1 hybrids were of an intermediate type. Recordings of the summated receptor responses (EAGs) showed no significant difference between parental beetles and hybrids. Similar results were obtained in reciprocal crosses, eastern females with western males and the reverse. Thus, there was no indication that sex-linked alleles determined the specificity of the ipsdienol receptor cell. The ratio between (+) and (−) cells was 14∶6 in the hybrids compared to 1∶12 in the western and 9∶12 in the eastern populations.
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  • 45
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    Journal of chemical ecology 11 (1985), S. 1249-1261 
    ISSN: 1573-1561
    Keywords: Pinus ponderosa ; Dendroctonus brevicomis ; pheromone ; attractant ; interruptant ; exo-brevicomin ; frontalin ; Coleoptera ; Scolytidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract After living ponderosa pines were baited with either female-infested bolts or synthetic pheromones,Dendroctonus brevicomis were caught on sticky screens throughout trapping periods of 15–46 days; however, large numbers of beetles were trapped during only a small portion (5–10 days) of these trapping periods. The most attractive portions of trees attacked contained 3–6 beetles dm2, in galleries ca. 2 cm long. Catch increased following addition of males to female-infested bolts, supporting the hypothesis that male-produced frontalin is an attractive pheromone of the western pine beetle. Catch at bolts removed from trees under attack was strongly dependent upon levels of boring activity. We found no evidence of interruption of the response to attractants during host colonization.
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  • 46
    ISSN: 1573-1561
    Keywords: Sex pheromone ; Lasioderma serricorne F. ; cigarette beetle ; Coleoptera ; Anobiidae ; serricornin ; polyketide biosynthesis
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A chemical study of the sex pheromone of the cigarette beetle was carried out. Seven components were isolated from active fractions of column chromatography of the female extract, and their structures were elucidated by spectroscopic evidence and confirmed by synthesis to be (4S,6S,7S)-4,6-di-methyl-7-hydroxynonan-3-one (serricornin) (I), 2,6-diethyl-3,5-dimethyl-3,4-dihydro-2H-pyran (anhydroserricornin) (II), 4,6-dimethylnonan-3,7-dione (III), 4,6-dimethylnonan-3,7-diol (IV), 4,6-dimethyl-7-hydroxy-4-nonen-3-one (V), (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(l-methyl-2-oxobutyl)-4H-pyran-4-one (serricorone) (VI) and (2S,3R)-2,3-dihydro-3,5-dimethyl-2-ethyl-6-(1-methyl-2-hydroxybutyl)-4H-pyran-4-one (serricorole) (VII). These structural features suggested that the occurrence of these components might be related to the polyketide biosynthesis. The behavioral bioassay and BAG experiments revealed the biological role of each component in the copulatory behavior of this insect.
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  • 47
    ISSN: 1573-1561
    Keywords: Electroantennogram ; grape borer ; Xylotrechus pyrrhoderus ; Bates ; Coleoptera ; Cerambycidae ; male sex pheromone ; (2S,3S)-octanediol ; (2S)-hydroxy-3-octanone ; optical isomers
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Electroantennograms were recorded from the grape borerXylotrechus pyrrhoderus in response to serial dilutions of male sex pheromone components, (2S,3S)-octanediol and (2S)-hydroxy-3-octanone, and to 100 μg of their optical isomers and host plant substances. Female antennae always responded more strongly than male antennae. Antennae of both sexes were highly sensitive to (2S)-hydroxy-3-octanone. F/M ratio (female to male EAG value) was greater for male sex pheromone components, especially (2S,3S)-octanediol, and their optical isomers than plant substances. Antennal sensitivity to optical isomers (2R,3R-octanediol and 2S,3R-octanediol) was lower than true pheromone components.
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  • 48
    ISSN: 1573-1561
    Keywords: Coleoptera ; Staphylinidae ; Deleaster dichrous ; defensive secretion ; gland system ; iridodial adhesive ; isopropyl esters ; sec-butyl esters
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The phylogenetically primitive rove beetleDeleaster dichrous (Grav.) (Oxytelinae) has been shown for the first time to possess two pairs of neighboring abdominal glands which are depleted simultaneously on molestation. The morphology of these glands is described. The defensive constituents of theDeleaster glands were elucidated directly from the mixtures by gas chromatographic-mass spectroscopic methods and microchemical reactions. The paired whitish glands secrete iridodial, which polymerizes on exposure to air to form an adhesive that probably deters small predatory arthropods. The red gland system ofD. dichrous contains the toxicp-toluquinone and a variety of isopropyl andsec-butyl esters. Artificial quinoid ester mixtures simulating the secretion ofD. dichrous showed only weak effects on mortality ofLucilia larvae in comparison with more effective secretions of phyiogenetically derived Oxytelinae. The secretion of the primitive genusDeleaster is characterized chemotaxonomically by β, γ-unsaturated C12 acids and esters, which are postulated as precursors for the characteristic defensive compounds of the derived species, thus indicating a clear evolutionary trend at the micromolecular level.
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  • 49
    ISSN: 1573-1561
    Keywords: Cryptolestes turcicus ; Coleoptera ; Cucujidae ; aggregation pheromone ; macrolide ; (Z,Z)-5,8-tetradecadien-13-olide ; (Z)-5-tetradecen-13-olide ; enantiomeric synergism
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    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Two biologically active macrolides were isolated from Porapak Q-captured beetle and frass volatiles ofCryptolestes turcicus (Grouvelle) and identified spectroscopically as (Z,Z)-5,8-tetradecadien-13-olide (I) and (Z)-5-tetradecen-13-olide (II). Natural I was active alone and was synergized by inactive II. The pheromones were male-produced but attractive to both sexes. Pheromone production increased dramatically when insects were aerated on a food source. Pure (R)- and (S)-I were inactive, but mixtures of (R)- and (S)-I were active, the first reported instance of enantiomeric synergism in the Cucujidae.
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  • 50
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    Chromatographia 20 (1985), S. 587-590 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion-pair chromatography ; Sulfonate pairing ion ; Adsorption isotherms
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    Topics: Chemistry and Pharmacology
    Notes: Summary The retention of positively and negatively charged and neutral solutes was studied in an aqueous phosphate buffer eluent, with constant inorganic-counterion concentration, on ODS-Hypersil stationary phase in the presence of various sulfonic acid ion-pairing reagents. The adsorption isotherms of the ion-pairing reagents d-camphor-10-sulfonic acid, sodium cyclohexylsulfamic acid and sodium alkylsulfonates (butyl-, hexyl- and octyl-) were determined by the breakthrough method.
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  • 51
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    Chromatographia 20 (1985), S. 615-617 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Vitamin B2 in food ; Column switching ; Liquid-solid extraction
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    Topics: Chemistry and Pharmacology
    Notes: Summary Vitamin B2 was enriched by liquid-solid extraction from large volumes of aqueous samples on a short precolumn. The enriched compounds were transferred onto an analytical reversed-phase column and separated by ion-pair chromatography. The equipment used provides the possibility of automation for routine analysis.
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  • 52
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Controlled-porosity glasses ; Chemically bonded phases ; Boron-glass surface enriched
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    Topics: Chemistry and Pharmacology
    Notes: Summary In the preparation of C18-bonded phases higher coverage densities were obtained using dimethylaminodimethyl-n-octadecylsilane than chlorodimethyl-n-octadecylsilane as the reagents. The HPLC results show the very high hydrophobicity of the materials obtained. The elution mechanism has been found to be independent of the coverage density on the boron-enriched glass surface in the range 2.3–4.0 μmol/m2.
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  • 53
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Direct injection of biological samples ; New quinitidine metabolites ; Deproteinisation on precolumn ; Column switching
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    Topics: Chemistry and Pharmacology
    Notes: Summary New quinidine metabolites, including 10,11-dihydrodiol quinidine N-oxide, 10,11-dihydrodiol quinidine and their glucuronides, were found in human urine. A quinidine monitoring HPLC method including these metabolites, is proposed by the direct injection of body fluid samples onto the precolumn for deproteinization followed by reverse phase separation in the analytical column with a column switching technique. The recovery of spiked quinidine and its metabolites in plasma was quantitative (98–102%) with good reproducibility (C.V.: 1.6–4.0%). Several clinical samples such as whole blood and urine were analyzed by the present method.
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  • 54
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Quantitative structure-retention relationships (QSRR) ; CNDO/2-MO Calculations
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    Topics: Chemistry and Pharmacology
    Notes: Summary Retention data for 12 aromatic test solutes with functional groups of various polarities were studied on a wellcharacterized monomeric octadecyl stationary phase over a range of methanol/water compositions. CNDO calculations on the solute structures and regression analysis indicated that two terms, the total energy, ET, and the maximal difference of electron excess charge, Cd, correlated well with changes in retention as a function of methanol composition. This approach allowed for the non-empirical calculation of retention data for solutes with a range of polarities, overcoming previous deficiencies in the estimation of molecular polarity for non-homologous solutes based on total dipole moment.
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  • 55
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Weak cation-exchanger ; Styrene-divinylbenzene copolymer
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    Topics: Chemistry and Pharmacology
    Notes: Summary A weak cation-exchanger for high-performance liquid chromatography is obtained by oxidation of either poly(methylstyrene-divinylbenzene) or of poly(chloromethylstyrene-divinylbenzene). Reaction conditions were optimised to yield an exchange capacity of about 4meqg−1 dry resin. The material was evaluated chromatographically as a function of pH, organic modifier, temperature and flow rate. A combination of ionexchange and hydrophobic interaction between the solutes and the packing material was observed. This could be used to provide more options for realising chromatographic separations. Some chromatograms of heterocyclic bases, nucleosides, nucleotides and amino acids are shown.
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  • 56
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    Chromatographia 20 (1985), S. 87-96 
    ISSN: 1612-1112
    Keywords: Time Optimization ; Column liquid chromatography ; Microbore ; Theophylline
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    Topics: Chemistry and Pharmacology
    Notes: Summary Algorithms for the time optimization of an HPLC separation are presented. Resolution, column performance, extra-column variance, capacity factor, and column length are incorporated into these algorithms. Extracolumn variance for a high-speed microbore system (1 mm i. d. column) was assessed using 2nd moment variance and a non-linear extrapolation of tubing length to zero. Extra-column variance, as a function of flowrate, was incorporated into the reduced operating curve of column performance. The use of empirical correction factors for column reproducibility and homogeneity are suggested. Cutting to an optimum length did not degrade column performance. These algorithms were applied to the optimization of a microbore assay for theophylline, in a simple xanthine mixture. Resulting total analysis times were reduced to 10seconds per sample, at a flowrate of 700μl/min.
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  • 57
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Metal complexes ; Tetrakis(4-methylphenyl)porphine
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    Topics: Chemistry and Pharmacology
    Notes: Summary The feasibility of reversed-phase high-performance liquid chromatography for the separation of several metal complexes ofmeso-tetrakis(p-tolyl)porphine (TTP) is described. A combination of an octadecyl-bonded stationary phase with a non-aqueous polar mobile phase, such as an acetone-acetonitrile mixture, has proved effective for the separation. Thus, the TTP complexes of Mg, VO, Ni, Cu, Zn, and Pd and also TTP free acid were successfully separated in about 10min on a Li-Chrosorb RP-18 column (7μm, 250×4mm i.d.) with a 70∶30 (vol/vol) mixture of acetone and acetonitrile at a flow-rate of 1 mlmin−1.
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  • 58
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    Chromatographia 20 (1985), S. 213-218 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Nitro-PAHs ; Diesel particulate extract ; Column switching-HPLC ; Pyrene-butyric acid stationary phase ; π-acceptor ligands
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    Topics: Chemistry and Pharmacology
    Notes: Summary A method is described for the determination of nitrated polynuclear aromatic hydrocarbons (nitro-PAHs), in particular 1-nitropyrene, in diesel particulate extracts. The method employs a multidimensional HPLC (column switching) technique with final on-line peak identification by UV-VIS spectral comparison with standards. To achieve exceptional chromatographic selectivity for nitro-PAHs, a new pyrene butyric acid amide phase has been prepared which is capable of forming donor-acceptor complexes with them. With this technique it is possible to confirm the presence of 1-nitropyrene in the range 3–100 ng/mg on filter-collected diesel soot. Its utility was demonstrated with diesel exhaust extracts spiked with varying levels of 1-nitropyrene and proved to be highly selective.
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  • 59
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Microcapillary column ; Gasoline group analysis ; Conventional IR detection
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    Topics: Chemistry and Pharmacology
    Notes: Summary Slurry-packed microcapillary column liquid chromatography with conventional infrared detection is described for the group-type analysis of gasolines. The results indicate that the three eluted groups, saturates, olefins and aromatics, from the microcapillary column are easily detected by conventional microcomputerized infrared spectrometer coupled with a Teflon flow-cell with a good signal-to-noise ratio. This study shows the feasibility of microcapillary column liquid chromatography combined with a low-cost, conventional infrared spectrometer as a routine tool which allows the analyst to use an LC-IR system effectively and economically.
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  • 60
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    Chromatographia 20 (1985), S. 425-433 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reversed phase ; Adsorption isotherm ; Dead volume
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    Topics: Chemistry and Pharmacology
    Notes: Summary In RPLC the dead volume can be defined as the difference between the maximum column hold-up volume and the volume of the adsorbed phase. The composition of the adsorbed phase depends on the composition of the mobile phase and therefore, the dead volume also varies with it. In this work, the alkyl bonded phase acetonitrile (ACN)-water mobile phase system is investigated. In the system, deuterated water (D2O) and deuterated acetonitrile (D-ACN) are retained due to the isotopic dilution effect. By means of D2O and D-ACN, the absolute adsorption isotherm of the organic modifier ACN is measured. Based on the isotherm, the chromatographic behaviour of ACN, D-ACN and D2O, the variation of the dead volume with the composition of the mobile phase, and the approach to determine the maximum column hold-up volumn are explained. In addition, the various approaches to determine the dead volume are compared and the recommendations are given for the case of common unbuffered binary systems (MeOH/H2O, THF/H2O and ACN/H2O).
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  • 61
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amiloride hydrochloride ; Hydrochlorothiazide ; Quantitative determination
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    Topics: Chemistry and Pharmacology
    Notes: Summary A procedure for the simultaneous quantitative determination of amiloride hydrochloride and hydrochlorothiazide by high-performance liquid chromatography is proposed. A reversed-phase LiChrosorb C8 stationary phase is used. The eluent consisted of an acetonitrile/0.1M phosphate buffer pH3 (15∶85) mixture, containing 50mM propylamine hydrochloride. In this system amiloride hydrochloride, a basic drug, eluted with a acceptable asymmetry factor (Asf=2.1). A simple extraction procedure with methanol is used. Relative standard deviations of 0.87% and 1.6% were obtained for amiloride hydrochloride and hydrochlorothiazide respectively. Chlorothiazide, a thiazide diuretic, is a suitable internal standard. Furthermore the method is also specific for other thiazide diuretics, potassium-sparing diuretics and loop diuretics and for the respective hydrolysis productes of both drugs. Analysis time is reduced to a minimum; the chromatographic separation is complete within 6 minutes.
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  • 62
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    Chromatographia 20 (1985), S. 495-499 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; L-tryptophan-serum albumin binding ; Bovine serum albumin ; Human serum albumin ; Binding parameters
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Two high-performance liquid chromatography (HPLC) techniques were developed for the determination of binding constants in the interaction of serum albumin with L-tryptophan: internal calibration and external calibration. The results obtained were compared with those obtained by the classical method of equilibrium dialysis and by gel filtration. While all the methods are equally reliable, the internal and external calibration techniques seem to be superior in their simplicity, speed and convenience.
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  • 63
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    Chromatographia 20 (1985), S. 529-532 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Modified silica gels ; Pyrimidines
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    Topics: Chemistry and Pharmacology
    Notes: Summary The effect of the surface chemistry of bonded-phase column material containing alkyl, phenyl, cyano and amino groups on the adsorption of pyrimidine molecules has been studied by HPLC. The dependence of the retention on the chemical structure of the adsorbed molecules was determined. The influence of the substituents at the pyrimidine ring and their position on the retention character is shown for various bonded phases.
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  • 64
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    Chromatographia 20 (1985), S. 559-565 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Reaction detector ; Formaldehyde determination ; Trace analysis ; Cosmetic products
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The determination of free formaldehyde in the presence of its donators in cosmetic samples by a combination of reversed phase chromatography and post column reaction detection is described. The free formaldehyde is separated on a RP column with water as eluent from interfering formaldehyde-containing compounds and consecutively determined by the lutidine method in a reaction detector with knitted open tubes. With detection in the visible (420nm) the minimum detectable quantity is 40 ppb, with fluorimetric detection 15 ppb. The sample clean-up procedure for cosmetic products ranging from mascara to shampoo is by extracting the formaldehyde with water of pH 3, where the decomposition rate of the donators is minimal. Smaller amounts of free formaldehyde are always found compared to the standard lutidine method.
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  • 65
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; FTIR detection ; Aqueous eluents ; Deuterated compounds
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    Topics: Chemistry and Pharmacology
    Notes: Summary Deuterated compounds have been used as mobile phases for microcolumn high-performance liquid chromatography (HPLC) employing flow-cell Fourier transform infrared spectroscopy for detection. Separations were carried out on adsorption, reversed-phase, non-aqueous size-exclusion and aqueous size-exclusion chromatographic columns. Due to the IR transparency of deuterated compounds in a C−H stretching region they represent nearly ideal eluents in terms of universal detection. In addition, due to the shift in the absorption wavenumber following deuteration, deuterated solvents allow FTIR detection of solutes in other regions, where otherwise it would be prohibited, or sensitivity sacrified by interfering solvent absorption.
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  • 66
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Retention volumes ; ODS silica ; Aromatic compounds ; Substituent interaction effect
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    Topics: Chemistry and Pharmacology
    Notes: Summary Retention volumes of monosubstituted benzenes, benzoic acids, phenols and anilines have been measured in reversed-phase liquid chromatography. Buffered acetonitrile-water and tetrahydrofuran-water eluents were used with an octadecylsilylsilica adsorbent. From the net retention volumes a substituent interaction effect was calculated and described with the linear free energy relationship developed by Taft. The positive sign of the values of the ρ-parameters, figuring in this relationship, was interpreted in terms of hydrogen bonding between the solutes and the eluent.
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  • 67
    ISSN: 1612-1112
    Keywords: Donor-acceptor complexes ; Column liquid chromatography ; Caffeine bonded phase ; 7(n-propyl)theophylline silica ; Petroleum residues and asphalts
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    Topics: Chemistry and Pharmacology
    Notes: Summary The preparation of a new caffeine phase for HPLC is described. The capacity ratios (k′) of about ten polyaromatic hydrocarbons have been determined. It has been shown that the aromatics were eluted according the number of rings, only slightly influenced by the substituents. The performance of the stationary phase is demonstrated with separations of petroleum asphalts and residues and aromatic mixtures.
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  • 68
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    Chromatographia 20 (1985), S. 179-184 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Ion chromatography ; Potentiometric detection ; Copper electrode
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    Topics: Chemistry and Pharmacology
    Notes: Summary A metallic copper electrode housed in a suitable flowcell is shown to be a sensitive and versatile potentiometric detector for ion chromatography. This electrode may be used for direct or indirect detection of many inorganic anions and cations and also for organic acids. In the direct detection mode, electrode response is based on either complexation of copper ions at the electrode surface by eluted species, or on oxidation and reduction reactions for eluted species which are strong oxidants or reductants. Direct detection is therefore applicable to such species as amino acids, organic acids, chloride, bromide, iodide, chlorate, bromate and iodate. Indirect detection is possible for anions which do not complex copper ions, provided a copper complexing ligand (such as phthalate) is used in the eluent; cations which complex this ligand are also detectable. Indirect detection may be used for species such as nitrite, nitrate, acetate, formate, succinate, benzoate, alkaline earth ions and transition metal ions. Electrode calibration relationships are discussed and sample separations are presented, together with some typical detection limits attainable in the direct and indirect detection modes.
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  • 69
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    Chromatographia 20 (1985), S. 239-241 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Bonded phases ; Anthracene silica gel
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    Topics: Chemistry and Pharmacology
    Notes: Summary N(9-methylanthracene)aminopropyl silica gel is introduced as a new reversed-phase packing material. It has specific selectivity for some aromatic compounds. In this paper the anthracene phase is compared with commercial octadecyl-, phenyl- and aminopropyl-bonded silica gels.
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  • 70
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Amino silica gel ; Neuraminic acids ; UV detection at nanomole level
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    Topics: Chemistry and Pharmacology
    Notes: Summary Neuraminic acid derivatives were separated easily by liquid chromatography on amino phases and using acetonitrile/15 mM phosphate buffer, pH 5.2 as mobile phase. Detection at 200 nm allowed determination of substances in the nanomole range. All solvent systems were used isocratically at room temperature. The separation did not depend on ion-exchange but on a partition mechanism, the solutes being separated according to their polarity. Thus, it was possible to optimize the resolution by varying the stationary phase and the composition of the eluent.
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  • 71
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Phenyl bonded phases ; Effect of pore size on retention ; Polycyclic aromatic hydrocarbons ; Silica supports
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    Topics: Chemistry and Pharmacology
    Notes: Summary Differences in bonded phase properties were studied for triphenyl, diphenyl, phenyl and benzyl phases prepared on a variety of silicas. A total of six silicas with pore diameters ranging from 100 to 200 Å were used in the synthesis. The effect of the pore diameter of the silicas on the retention of polycyclic aromatic hydrocarbons are discussed. Differences in retention were observed as a function of pore size, but not much difference was observed with substrates having pore sizes larger than about 170Å. The observed phenomena are explained by two steric exclusion mechanisms, one during the bonding reaction, and the other in the chromatographic analysis. Statistical calculations were performed using the descriptors showing molecular size and/or shape. The results indicated that the difference between bulky phases and less bulky phases was only observed in the degree of shape-recognition ability of the solute while no differences exist in the retention mechanisms on the different phases.
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  • 72
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    Chromatographia 20 (1985), S. 303-307 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Size-exclusion ; Dynamic equilibrium ; Ion-pairing interaction ; Monomer-dimer separation
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    Topics: Chemistry and Pharmacology
    Notes: Summary Molecular interaction between uni-uni valent ions and bovine serum albumin was investigated by size-exclusion chromatography. Elution profiles are first presented for salt and protein solutions as samples with water as the mobile phase; then for water and protein as samples with salt solutions as the mobile phase. The results suggest the existence of a dynamic equilibrium between the salt ions and the protein ions as reactants and the ion-pair (salt-protein) complex as a product.
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  • 73
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    Chromatographia 20 (1985), S. 471-476 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Organic polyselenides ; Molecular area effects ; Comparison with polysulphides
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    Topics: Chemistry and Pharmacology
    Notes: Summary Organic polyselenides in which the selenium chains are terminated at both ends by ethyl-thio, butyl-thio, phenylthio, or phenyl groups were prepared. Their chromatographic behavior in HPLC on a bonded octadecyl phase with entirely or mainly methanolic eluents was investigated and compared with the corresponding polysulphides. The retention increment per Se atom is greater than that for S atoms. The ratio of Se to S increments is equal to the ratio of surface area increments. The S−Se bond does not have an appreciable influence on retention. Bonded to phenyl, selenium increases retention to the same extent as sulphur does. Some of the RSSenSR solutes were identified by mass spectrometry and other techniques.
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    Chromatographia 20 (1985), S. 13-19 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Open tubes ; Diffusion coefficient ; Calibration curve for oligostyrenes ; Diffusion-averaged molecular weight ; Polydispersity
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    Topics: Chemistry and Pharmacology
    Notes: Summary The concept of a diffusion-averaged molecular weight, Md′ is presented, and Md is defined for polydisperse samples. It is shown via oligostyrene mixtures that Md can be determined in 20 minutes with common chromatographic equipment. If Md is measured and Mn or Mw is known, the polydispersity can be obtained.
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  • 75
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Silica gel solubility ; Copper (II) silica gel solubility ; Copper (II) silica gel stability
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary After summarizing published results on silica gel and alkyl-bonded silica gel solubilities, the experimental solubility of unmodified silica and copper silicate gel (used in ligand exchange chromatography) in watermethanol-ammonia and water-acetonitrile-ammonia mixtures are given. These results demonstrate that silica gel solubility, measured by a static method, varies greatly with the water volume fraction of a ternary mixture. Curiously, no influence from the organic nature of the solvent was demonstrated. This observation is inconsistent with the fact that the copper silicate gel used in ligand-exchange chromatography with water-methanol-ammonia as mobile phase is attacked more rapidly than with water-acetonitrile-ammonia. An explanation based upon the variations of acid-base properties of silicic acid versus mobile phase dielectric constant values in conjunction with the methanol protophilic properties is proposed. Finally, it is shown that chromatographic columns filled with copper silicate gel have lifetimes of several months, if they are used with a procolumn (of copper silicate gel) and with acetonitrile as organic solvent with a volume fraction greater than 0.5 in the mobile phase.
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  • 76
    ISSN: 1612-1112
    Keywords: Hydrolysis, high temperature ; Column liquid chromatography ; Ion-exchange ; Cellulose ; Oligomeric and monomeric sugars
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The hydrolysis of different cotton materials under hydrothermal conditions was investigated. For the analysis of the resulting reaction products high-performance liquid chromatography and gel-permeation chromatography were applied. HPLC columns with ion exchange materials as stationary phases (HPX 87P and Shodex S801) enabled the separation of monomeric sugars and degradation products. Oligomeric sugars were analyzed using a gel column (Bio-Gel P-2) as well as a HPLC column (HPX 42A). Through identification of additional reaction products the mass balance of the hydrolysis can be improved and the analysis of the distribution of the oligomeric sugars gives information for the selection of the reaction conditions.
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  • 77
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    Chromatographia 20 (1985), S. 96-98 
    ISSN: 1612-1112
    Keywords: Column liquid chromatography ; Phthalic anhydride ; Naphthoquinones
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple method of analysis of the 1,2 and 1,4 isomers of naphthoquinone in crude phthalic anhydride has been developed. The sample was first dissolved in water at 60°C to quantitatively hydrolyse the anhydride to phthalic acid. Analysis of the aqueous solution by reversed-phase HPLC using 75∶25 methanol:water mobile phase resulted in excellent resolution between the phthalic acid and the naphthoquinones and enabled quantitative measurement of each of the naphthoquinones to 0.1 % in crude phthalic anhydride.
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  • 78
    ISSN: 1573-1561
    Keywords: Olfaction ; receptor cell ; chirality ; perception ; neurobiology ; pheromone ; enantiomer ; bark beetle ; electrophysiology ; Douglas-fir beetle ; Dendroctonus pseudotsugae ; Coleoptera ; Scolytidae ; (+)-frontalin ; (−)-frontalin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Olfactory perception of pheromonal enantiomers by male and female Douglas-fir beetles,Dendroctonus pseudotsugae Hopk. (Coleoptera: Scolytidae), was investigated by electrophysiological techniques and behavioral bioassays. Electroantennograms (EAGs) and single-cell responses indicated both sexes to be more responsive to racemic frontalin and the (−)-enantiomer at lower dosages. At higher dosages, little difference was noted in responses to either enantiomer. However, response to the racemic mixture at higher dosages was slightly greater than responses to either enantiomer alone. In laboratory behavioral bioassays, responses to low concentrations of (−)-frontalin and the racemic mixture exceeded response to the (+)-enantiomer alone. At a higher concentration, responses to the racemic mixture or either enantiomer alone did not differ. The results indicate that separate enantiomer-specific acceptors may exist on the same pheromone receptor cell.
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  • 79
    ISSN: 1573-1561
    Keywords: Tribolium castaneum ; Coleoptera ; Tenebrionidae ; red flour beetle ; olfactory behavior ; ethyl 9,12-octadecadienoate ; methyl octadecanoate ; methyl tetradecanoate ; methyl pentadecanoate ; ethyl tetradecanoate ; ethyl pentadecanoate ; ethyl octadecanoate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract The olfactory responses of red flour beetles,Tribolium castaneum (Herbst), to methyl and ethyl ester of C14–C18 fatty acid prepared from tallow were studied. Methyl octadecanoate and ethyl octadecanoate discouraged aggregation of beetle adults. Ethyl 9.12-octadecadienoate acted as a repellent. Methyl pentadecanoate and ethyl tetradecanoate induced copulation at the level of 5 × 102 and 2 × 103 μg, respectively. The maximum response was observed at the level of 5 × 102 μg of the same compounds, and these compounds appear to stimulate males only.
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  • 80
    ISSN: 1573-1561
    Keywords: Boll weevil ; Anthonomus grandis ; Coleoptera ; Curculionidae ; feeding stimulants ; cotton buds ; anthers ; phytol ; geranylgeraniol esters ; phytol oleate ; phytol dodecanoate
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Column chromatography of the pentane extract of freeze-dried cotton buds or anthers yielded a wax-sterol ester fraction that exhibited potent feeding stimulant activity for the cotton boll weevil. The waxes of the wax-sterol ester mixture were responsible for the feeding activity. Saponification of the wax-sterol ester fraction yielded about 15% alcohols and 85% sterols. A C18∶1 alcohol, dihydrophytol, phytol, and geranylgeraniol constituted 15, 36, 26, and 23%, respectively, of the total alcohols, implicating certain of their long-chain esters as feeding stimulants. Several esters of dihydrophytol, phytol, and geranylgeraniol were identified among the waxes by GC-MS. Certain phytol, geranylgeraniol, and oleyl alcohol esters containing C12 to C26 acid moieties were synthesized and were found to induce high feeding stimulant activity in the cotton boll weevil.
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  • 81
    ISSN: 1573-1561
    Keywords: Aggregation pheromone ; attractant ; (R * S *)-5-hydroxy-4-methyl-3-heptanone ; (R * R *)-5-hydroxy-4-methyl-3-heptanone ; sitophilure ; Sitophilus oryzae ; S. zeamais ; S. granarius ; Coleoptera ; Curculionidae
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract A male-produced aggregation pheromone, common to the rice weevil,Sitophilus oryzae, and the maize weevil,S. zeamais, was isolated and identified from hexane extracts of highly absorbent paper disks exposed individually to young virgin male weevils. A combination of preparative column and gas-liquid chromatography of disk extracts yielded purified natural pheromone. When analyzed by nuclear magnetic resonance spectroscopy and gas chromatography-mass spectrometry, the structure of the natural pheromone, “sitophilure,” proved to be (R *,S *)-5-hydroxy-4-methyl-3-heptanone, of unknown enantiomeric composition. Synthetic racemic pheromone was highly attractive to males and females of both rice and maize weevils. In addition, both sexes of the granary weevil,S. granarius (L.) were attracted to the racemic preparation.
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  • 82
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    Journal of chemical ecology 11 (1985), S. 1307-1321 
    ISSN: 1573-1561
    Keywords: Cucurbitacins ; Diabrotica spp. ; Acalymma vittatum ; Coleoptera ; Chrysomelidae ; kairomone metabolism ; detoxification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Chemistry and Pharmacology
    Notes: Abstract Five species of diabroticites with different host-plant preferences produced an essentially identical array of metabolites when fed radiolabeled cucurbitacin B synthesized in vivo and purified fromCucurbita maxima Duchesne seedlings. All species excreted the bulk of the cucurbitacin (67,17-94.59% total dpm), permanently sequestered a small proportion of a cucurbitacin conjugate in the hemolymph (0.98–2.76%), and apportioned the remainder between the gut, the body, and the eggs (when present). Markedly different ratios between the excretory metabolites (i.e., polar vs. unmetabolized cuc) suggest thatDibrotica virgifera virgifera, a grass specialist, andAcalymma vittatum, a cucurbit specialist, have lower rates of metabolic alteration than the polyphagousD. undecimpunctata howardi, D. balteata, andD. cristata, which is associated with relict prairies. Mean life-spans ofD. balteata and D. v. virgifera and maleA. vittatum decreased significantly with continuous feeding onCucurbita fruit containing cucurbitacins (vs. fruit devoid of cucs). The longevity of femaleA. vittatum, however, was unaffected by the presence of cucurbitacins.
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