Thermochemical properties of benzoic acid derivatives VIII. Enthalpies of combustion and formation of o-, m-, and p- t-butylbenzoic acids

The enthalpies of formation in the crystalline state at 298.15 K of o-, m-, and p-t-butyl-benzoic acids have been determined by static-bomb calorimetry. Vapour-pressure determinations were made by the Knudsen-effusion technique and the sublimation enthalpies at the mean temperatures of the measurement ranges have been derived for the three acids. The values obtained are:

     

982.

Massenspektren neuer Phloroglucide,insbesondere solcher mit Valerylseitenketten     

M. Lounasmaa  C.-J. Widn  T. Reichstein 《Helvetica chimica acta》1973,56(3):1133-1144

Mass spectra of phloroglucinol derivatives recently isolated from African Dryopteris species are presented. Phloroglucides with n-valeryl side chain were found in these ferns for the first time. In the mass spectra they show strong peaks corresponding to loss of propene (C₃H₆) produced by McLafferty rearrangement, as shown in model compounds. Aside of the rottleron change (discussed formerly) this must be considered in order to avoid wrong interpretation, particularly when mass spectra are used to analyse mixtures of homologues, as usually present in the plants. If valeryl side chains are present other methods must be used therefore to measure the amount or show the absence of lower homologues with acetyl side chains.     

983.

A flow injection-ETAAS system for the on-line determination of total and dissolved silica in waters     

Burguera M  Burguera JL  Carrero P  Rondón C 《Talanta》2002,58(6):1157-1166

In this work total (Si-tot) and ‘soluble’ or reactive (Si-sol) concentrations of silicon in natural and tap waters were sequentially determined by electrothermal atomic absorption spectrometry (ETAAS). First, samples were on-line diluted based on the merging-zone principle in order to allow the determination of Si-tot within the 300–1000 μgSi l⁻¹ range. After the dilution process, a sub-sample was collected in the capillary of a sampling arm assembly (SAA). Thereafter, samples were subject to a precipitation/dissolution process in order to allow the determination of Si-sol within the 280–850 μgSi l⁻¹. Si-sol was precipitated with ammonium chloride and collected on the walls of a knotted coil. The precipitate was dissolved with ammonium molybdate in an acidic medium (HNO₃) and a sub-sample was then collected in the SAA. In both cases, 10 μl volumes of the sub-sample were injected into the atomizer with the previous introduction of 20 ng of Eu as chemical modifier (10 μl) by the spectrometer autosampler. The recovery values obtained with natural waters spiked samples were over 46% and the agreement between observed and certified samples values was good. The proportion of Si-sol in comparison with the Si-tot was high (85–95%) in most natural waters. The precision of the method was 2.4–3.5 and 4.5–6.2% (n=10) for the determination of Si-tot and Si-sol, respectively.     

984.

Adsorption of N-Nitrosodiethylamine and N-Nitrosodimethylamine on Activated Carbon: A Pre-Concentration Procedure for Gas Chromatographic Analysis     

Sekar Fatma Aygün  Ahmet Uyanık  Bekir Batı 《Mikrochimica acta》2004,146(3-4):279-283

In this study, a rapid pre-concentration procedure, which employs powdered activated carbon as a clean-up and pre-concentration material, is described for the gas chromatographic analysis of N-nitrosodiethylamine (NDEA) and N-nitrosodimethylamine (NDMA) in aqueous solutions. It was found that powdered activated carbon is suitable for the adsorption of volatile N-nitrosamine compounds from aqueous solutions. Adsorption efficiency with spiked beer samples (alcohol content 5% v/v) was found to be 80.5% (NDMA) and 89.4% (NDEA) and recovery of extraction from activated carbon was calculated as 82.1% (NDMA) and 89.7% (NDEA), respectively. The effect of 100µgmL^–1 of tannic acid on the adsorption was also studied, and no significant effect on the adsorption and extraction of volatile N-nitrosamine compounds was found.     

985.

Micellar electrokinetic capillary chromatography method for direct determination of glucuronides of entacapone and its (Z)-isomer in human urine     

Lehtonen P  Lehtinen S  Mälkki-Laine L  Wikberg T 《Journal of chromatography. A》1999,836(1):173-188

This paper describes the validation of a micellar electrokinetic capillary chromatography method for the direct determination of the 3-O-glucuronides of entacapone and its (Z)-isomer, the main urinary metabolites of entacapone in humans. Entacapone is a novel drug which, as a potent inhibitor of catechol-O-methyltransferase (COMT), is used as an adjunct in the standard therapy of Parkinson's disease. The 3-O-glucuronide of another COMT inhibitor, nitecapone, was used as internal standard (I.S.). The validation experiments were performed by using spiked urine samples that were extracted with Sep-Pak C18 cartridges before analysis. Determinations were carried out in a buffer of pH 7.0 containing 25 mM of phosphate, 50 mM of borate and 20 mM of sodium dodecyl sulfate, and by applying 15 kV over a 67 cm (60 cm to the detector) x 75 microns fused-silica capillary. UV detection was at 335 nm. The validity of the method was assessed by investigating the identity of the analytes, selectivity, limit of quantitation, linearity, within-day precision, extraction recovery, between-day precision and accuracy, electroosmotic flow stability and analyte stability. The method proved to be reproducible, sufficiently selective and accurate. Extraction recoveries of the analytes were > 94%. The limit of quantitation (LOQ) was 2 micrograms/ml and the assay was linear in the range 2-150 micrograms/ml with correlation coefficients better than 0.999 for both glucuronides. The repeatability of the method, expressed as the ratio of corrected peak area of the analytes to that of I.S., gave RSD values of < 5% even at the LOQ. Between-day precision (RSD) was < 7.5% for both glucuronides at 7.5 micrograms/ml. Determination of the glucuronide concentrations in urine samples of 34 patients treated with entacapone either orally (200 mg) or intravenously (25 mg) showed the method to be suitable for monitoring the concentrations of the glucuronide of entacapone after both oral and intravenous administration and those of the glucuronide of its (Z)-isomer after oral administration. The limited long term stability of the system requires, however, frequent recalibration in applications involving long sample series.     

986.

Laser-excited molecular flourescence spectrometry for the determination of traces of nonmetals : Part 1. determination of traces of fluoride,chloride and bromide based on diatomic molecules in a graphite furnace     

Klaus Dittrich  Hans-Joachim Stärk 《Analytica chimica acta》1987

For the determination of flouride, chloride and bromide, a suitable metal ion is added in a modified graphite tube atomizer. After drying and ashing, the substances are vaporized and diatomic molecules between the metal and nonmetal are formed. These molecules are excited by a pulsed dye laser and the resulting fluorescence is measured. At constant metal concentration, the fluorescence is proportional to the halide concentration. The diatomic molecules used are MgF, InCl and AlBr. The detection limits are 11 pg of fluoride, 15 pg of chloride and 70 pg of bromide in the 10-μl injections, corresponding to 6 x 10^?8 mol l^?1 fluoride, 4 x 10^?8 mol l^?1 chloride and 9 x 10^?8 mol l^?1 bromides.     

987.

Aktivierungsanalytische Untersuchungen an hochreinem Silicium     

W. Gebauhr  J. Martín und E Haas 《Fresenius' Journal of Analytical Chemistry》1964,200(4):266-278

Zusammenfassung Zur Aktivierungsanalyse von hochreinem Silicium wurden die vermuteten Verunreinigungen in 3 Gruppen entsprechend der Halbwertszeit ihrer zur Bestimmung herangezogenen Radionuklide zusammengefaßt und für diese Gruppen chemisch-analytische Trennungsgänge ausgearbeitet. Damit war es möglich, in relativ geringen Probemengen etwa 30 Elemente zu bestimmen. Die dargelegten Ergebnisse liegen durchweg im oder unter dem ppb-Bereich (=10^–7 %).Zur Lokalisierung einiger Verunreinigungen wird die Autoradiographie herangezogen. Einige Aufnahmen zeigen, daß dieses Verfahren auch bei Vorhegen äußerst geringer Aktivitäten noch wertvolle Aussagen zu liefern vermag.

---

Summary For the activation analysis of high-purity silicon the supposed impurities are divided into 3 groups corresponding to the half-lives of the radionuclides belonging to the impurities. For these groups chemoanalytical separation schemes are developed. With this technique it was possible to determine about 30 elements in small samples. The results given are in or below the ppb-level.For localisation of the impurities autoradiography is used. Some of the pictures taken show, that also with very low activities valuable results can be obtained.

---

---

Zum Schlu mu die freundliche Hilfe erwähnt werden, die wir an den deutschen Reaktorstationen bei der Durchuürung der Bestrahlung rehalten haben. So sind wir der Reaktorstation Garching, insbesondere den Harren Dr. Köhler und Rau zu auerordentlichem Dank für die stats gewährte Unterstüzung bei der Bestrahlung der großen Zahl der Proben verpflichtet. — Die Analyse der kurzlebigen Radionuklide verlangte das Arbeiten direkt am Reaktor. Dank dem freundlichen Entgegenkommen der Herren Prof. Dr. E. Fischer und Dr. Röbert konnten wir dieses in einem Laboratorium der Reaktorstation Geesthacht durchführen, wobei wir auch den Herren Braun und Hauser für ihre bereitwillige Unterstützung zu danken haben.Schließlich sei Herrn Dr. Brandt für die Entwicklung der erwähnten Formel auch an dieser Stelle nochmals gedankt.

---

In gekürzter Form anläßlich der Tagung der Fachgruppe: Kern-, Radio- und Strahlenchemie der Gesellschaft Deutscher Chemiker in Heidelberg am 10. 9. 1963 vorgetragen.     

988.

Nickel-catalyzed Cyclotrimerization of Malononitrile: The Dicyanomethanide-bridged,Anionic NiII Complex [{Ni(C5F5)2(μ-NCCHCN)}2]2⊖     

Gregorio Lpez  Gregorio Snchez  Gabriel Garci  Jos Ruiz  Joaquín García  M. Martínez-Ripoll  A. Vegas  Juan A. Hermoso 《Angewandte Chemie (International ed. in English)》1991,30(6):716-718

     

989.

An nmr study of conformational exchange in some ketone-BF₃ and ether-BF₃ adducts     

J.S. Hartman  P. Stilbs  S. Forsén 《Tetrahedron letters》1975,16(40):3497-3500

     

990.

The effect of the "inert" counteranions in the deprotonation of the dihydrogen complex trans-[FeH(eta 2-H2)(dppe)2]+: kinetic and theoretical studies     

Basallote MG  Besora M  Durán J  Fernández-Trujillo MJ  Lledós A  Máñez MA  Maseras F 《Journal of the American Chemical Society》2004,126(8):2320-2321

Kinetic studies indicate that trans-[FeH(H2)(dppe)2]+ reacts with an excess of NEt3 to form cis-[FeH2(dppe)2] in a single kinetic step. The second-order rate constant is strongly affected by the presence of added salts, an acceleration being observed with BF4- and PF6- salts and a deceleration with BPh4-. Theoretical calculations indicate that the role of the accelerating anions consists of the formation of ion pairs that provide a more effective reaction pathway for deprotonation. However, for the ion pair with the bulky BPh4- anion, steric crowding in the proximities of the dihydrogen ligand hinders the approach of the base, and the reaction is decelerated.     

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	$\text{ΔH}{}_{\mathrm{f}}{}^{\mathrm{o}}\text{(c, 298.15 K)/kJ mol}{}^{\mathrm{?1}}$	$\text{ΔH}{}_{\mathrm{s}}\text{/kJ mol}{}^{\mathrm{?1}}$
o-t-butylbenzoic acid	476.2 ± 1.9	99.8 ± 0.4	(at 314.6 K)
m-t-butylbenzoic acid	504.3 ± 1.6	103.0 ± 0.5	(at 326.5 K)
p-t-butylbenzoic acid	502.9 ± 1.7	103.8 ± 0.4	(at 334.1 K)

Massenspektren neuer Phloroglucide,insbesondere solcher mit Valerylseitenketten

Mass spectra of phloroglucinol derivatives recently isolated from African Dryopteris species are presented. Phloroglucides with n-valeryl side chain were found in these ferns for the first time. In the mass spectra they show strong peaks corresponding to loss of propene (C₃H₆) produced by McLafferty rearrangement, as shown in model compounds. Aside of the rottleron change (discussed formerly) this must be considered in order to avoid wrong interpretation, particularly when mass spectra are used to analyse mixtures of homologues, as usually present in the plants. If valeryl side chains are present other methods must be used therefore to measure the amount or show the absence of lower homologues with acetyl side chains.     

A flow injection-ETAAS system for the on-line determination of total and dissolved silica in waters

In this work total (Si-tot) and ‘soluble’ or reactive (Si-sol) concentrations of silicon in natural and tap waters were sequentially determined by electrothermal atomic absorption spectrometry (ETAAS). First, samples were on-line diluted based on the merging-zone principle in order to allow the determination of Si-tot within the 300–1000 μgSi l⁻¹ range. After the dilution process, a sub-sample was collected in the capillary of a sampling arm assembly (SAA). Thereafter, samples were subject to a precipitation/dissolution process in order to allow the determination of Si-sol within the 280–850 μgSi l⁻¹. Si-sol was precipitated with ammonium chloride and collected on the walls of a knotted coil. The precipitate was dissolved with ammonium molybdate in an acidic medium (HNO₃) and a sub-sample was then collected in the SAA. In both cases, 10 μl volumes of the sub-sample were injected into the atomizer with the previous introduction of 20 ng of Eu as chemical modifier (10 μl) by the spectrometer autosampler. The recovery values obtained with natural waters spiked samples were over 46% and the agreement between observed and certified samples values was good. The proportion of Si-sol in comparison with the Si-tot was high (85–95%) in most natural waters. The precision of the method was 2.4–3.5 and 4.5–6.2% (n=10) for the determination of Si-tot and Si-sol, respectively.     

Adsorption of N-Nitrosodiethylamine and N-Nitrosodimethylamine on Activated Carbon: A Pre-Concentration Procedure for Gas Chromatographic Analysis

In this study, a rapid pre-concentration procedure, which employs powdered activated carbon as a clean-up and pre-concentration material, is described for the gas chromatographic analysis of N-nitrosodiethylamine (NDEA) and N-nitrosodimethylamine (NDMA) in aqueous solutions. It was found that powdered activated carbon is suitable for the adsorption of volatile N-nitrosamine compounds from aqueous solutions. Adsorption efficiency with spiked beer samples (alcohol content 5% v/v) was found to be 80.5% (NDMA) and 89.4% (NDEA) and recovery of extraction from activated carbon was calculated as 82.1% (NDMA) and 89.7% (NDEA), respectively. The effect of 100µgmL^–1 of tannic acid on the adsorption was also studied, and no significant effect on the adsorption and extraction of volatile N-nitrosamine compounds was found.     

Micellar electrokinetic capillary chromatography method for direct determination of glucuronides of entacapone and its (Z)-isomer in human urine

This paper describes the validation of a micellar electrokinetic capillary chromatography method for the direct determination of the 3-O-glucuronides of entacapone and its (Z)-isomer, the main urinary metabolites of entacapone in humans. Entacapone is a novel drug which, as a potent inhibitor of catechol-O-methyltransferase (COMT), is used as an adjunct in the standard therapy of Parkinson's disease. The 3-O-glucuronide of another COMT inhibitor, nitecapone, was used as internal standard (I.S.). The validation experiments were performed by using spiked urine samples that were extracted with Sep-Pak C18 cartridges before analysis. Determinations were carried out in a buffer of pH 7.0 containing 25 mM of phosphate, 50 mM of borate and 20 mM of sodium dodecyl sulfate, and by applying 15 kV over a 67 cm (60 cm to the detector) x 75 microns fused-silica capillary. UV detection was at 335 nm. The validity of the method was assessed by investigating the identity of the analytes, selectivity, limit of quantitation, linearity, within-day precision, extraction recovery, between-day precision and accuracy, electroosmotic flow stability and analyte stability. The method proved to be reproducible, sufficiently selective and accurate. Extraction recoveries of the analytes were > 94%. The limit of quantitation (LOQ) was 2 micrograms/ml and the assay was linear in the range 2-150 micrograms/ml with correlation coefficients better than 0.999 for both glucuronides. The repeatability of the method, expressed as the ratio of corrected peak area of the analytes to that of I.S., gave RSD values of < 5% even at the LOQ. Between-day precision (RSD) was < 7.5% for both glucuronides at 7.5 micrograms/ml. Determination of the glucuronide concentrations in urine samples of 34 patients treated with entacapone either orally (200 mg) or intravenously (25 mg) showed the method to be suitable for monitoring the concentrations of the glucuronide of entacapone after both oral and intravenous administration and those of the glucuronide of its (Z)-isomer after oral administration. The limited long term stability of the system requires, however, frequent recalibration in applications involving long sample series.     

Laser-excited molecular flourescence spectrometry for the determination of traces of nonmetals : Part 1. determination of traces of fluoride,chloride and bromide based on diatomic molecules in a graphite furnace

For the determination of flouride, chloride and bromide, a suitable metal ion is added in a modified graphite tube atomizer. After drying and ashing, the substances are vaporized and diatomic molecules between the metal and nonmetal are formed. These molecules are excited by a pulsed dye laser and the resulting fluorescence is measured. At constant metal concentration, the fluorescence is proportional to the halide concentration. The diatomic molecules used are MgF, InCl and AlBr. The detection limits are 11 pg of fluoride, 15 pg of chloride and 70 pg of bromide in the 10-μl injections, corresponding to 6 x 10^?8 mol l^?1 fluoride, 4 x 10^?8 mol l^?1 chloride and 9 x 10^?8 mol l^?1 bromides.     

Aktivierungsanalytische Untersuchungen an hochreinem Silicium

Zusammenfassung Zur Aktivierungsanalyse von hochreinem Silicium wurden die vermuteten Verunreinigungen in 3 Gruppen entsprechend der Halbwertszeit ihrer zur Bestimmung herangezogenen Radionuklide zusammengefaßt und für diese Gruppen chemisch-analytische Trennungsgänge ausgearbeitet. Damit war es möglich, in relativ geringen Probemengen etwa 30 Elemente zu bestimmen. Die dargelegten Ergebnisse liegen durchweg im oder unter dem ppb-Bereich (=10^–7 %).Zur Lokalisierung einiger Verunreinigungen wird die Autoradiographie herangezogen. Einige Aufnahmen zeigen, daß dieses Verfahren auch bei Vorhegen äußerst geringer Aktivitäten noch wertvolle Aussagen zu liefern vermag.

---

Summary For the activation analysis of high-purity silicon the supposed impurities are divided into 3 groups corresponding to the half-lives of the radionuclides belonging to the impurities. For these groups chemoanalytical separation schemes are developed. With this technique it was possible to determine about 30 elements in small samples. The results given are in or below the ppb-level.For localisation of the impurities autoradiography is used. Some of the pictures taken show, that also with very low activities valuable results can be obtained.

---

---

Zum Schlu mu die freundliche Hilfe erwähnt werden, die wir an den deutschen Reaktorstationen bei der Durchuürung der Bestrahlung rehalten haben. So sind wir der Reaktorstation Garching, insbesondere den Harren Dr. Köhler und Rau zu auerordentlichem Dank für die stats gewährte Unterstüzung bei der Bestrahlung der großen Zahl der Proben verpflichtet. — Die Analyse der kurzlebigen Radionuklide verlangte das Arbeiten direkt am Reaktor. Dank dem freundlichen Entgegenkommen der Herren Prof. Dr. E. Fischer und Dr. Röbert konnten wir dieses in einem Laboratorium der Reaktorstation Geesthacht durchführen, wobei wir auch den Herren Braun und Hauser für ihre bereitwillige Unterstützung zu danken haben.Schließlich sei Herrn Dr. Brandt für die Entwicklung der erwähnten Formel auch an dieser Stelle nochmals gedankt.

---

In gekürzter Form anläßlich der Tagung der Fachgruppe: Kern-, Radio- und Strahlenchemie der Gesellschaft Deutscher Chemiker in Heidelberg am 10. 9. 1963 vorgetragen.     

The effect of the "inert" counteranions in the deprotonation of the dihydrogen complex trans-[FeH(eta 2-H2)(dppe)2]+: kinetic and theoretical studies

Kinetic studies indicate that trans-[FeH(H2)(dppe)2]+ reacts with an excess of NEt3 to form cis-[FeH2(dppe)2] in a single kinetic step. The second-order rate constant is strongly affected by the presence of added salts, an acceleration being observed with BF4- and PF6- salts and a deceleration with BPh4-. Theoretical calculations indicate that the role of the accelerating anions consists of the formation of ion pairs that provide a more effective reaction pathway for deprotonation. However, for the ion pair with the bulky BPh4- anion, steric crowding in the proximities of the dihydrogen ligand hinders the approach of the base, and the reaction is decelerated.