<title>Electro-optical and fluorescence lifetime studies of aminophthalimide probes in liquids</title>

The modified electro-optical absorption and emission methods are described as well as their use for measurements of electrical dipole moments of five aminophthalimides in ground and excited states. It is found that there exists a principal difference between properties of 3- aminophthalimide (3AP) and 4-amino-N-methylphthalimide (4ANMP) in different solvents. The equilibrated dipole moment of 3AP in its excited state is practically independent on the solvent polarity, in comparison with 4ANMP. The possible mechanism of this effect is discussed.© (1995) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.

An immunoassay for terbutryn using direct hapten linkage to a glutaraldehyde network on the polystyrene surface of standard microtiter plates.

2-Aminobutylamino-4-ethylamino-6-isopropylamino-1,3,5-triazine (ABA-atrazine) has been synthesized and used as a coating hapten in an immunoassay with a monoclonal antibody against terbutryn. Coating was achieved by covalently linking ABA-atrazine to a glutaraldehyde polymer network directly bound to the polystyrene surface of a standard 96-well microtiter plate. The assay was carefully optimized. In particular, the coating hapten concentration had a strong effect on the ELISA sensitivity. By including a pre-incubation step a low test midpoint (IC50-value) of 0.130 microg L(-1) was achieved. As far as we are aware this is the most sensitive ELISA for terbutryn yet reported. The coating-hapt…

Dipole moments of 4′-aminoflavonols determined using electro-optical absorption measurements or molecular Stark-effect spectroscopy

The electro-optical absorption measurements (EOAM) were used to measure the dipole moments of the normal form of 4 � -(methoxy)-3hydroxyflavone (FOM), 4 � -(dimethylamino)-3-hydroxyflavone (FME), and 4 � -N-(15-azacrown-5)-3-hydroxyflavone (FCR). For these probes the excited state intramolecular proton transfer (ESIPT) takes place. For comparison, the dipole moments of 4 � -(dimethylamino)-3methoxyflavone (FME3ME), for which ESIPT is lacking, were measured. In the case of FCR, FME, and FME3ME the equilibrated ground (µg) and excited Franck–Condon state (µ FC ) electrical dipole moments are parallel to each other and also parallel to the transition dipole moment. The electrical dipole moment…

Detectors and Chromatography. Ed. by A.J.C. Nicholson. Pp viii + 198, Australian Scientific Industry Association, ISBN 0 949761 087

Oligo(phenylenevinylene)s with Terminal Donor–Acceptor Substitution This work was supported by the Deutsche Forschungsgemeinschaft and the Fonds der Chemischen Industrie.

Extraction of lapachol from Tabebuia avellanedae wood with supercritical CO2: an alternative to Soxhlet extraction?

The solubility of lapachol in supercritical CO2 was determined at 40°C and pressures between 90 and 210 bar. Supercritical fluid extraction of lapachol and some related compounds by CO2 from Tabebuia avellanedae wood is compared to Soxhlet extraction with different solvents. A standard macroscale (100-200 g wood) and a microscale (~10 mg wood) experimental setup are described and their results are compared. The latter involved direct spectrophotometric quantification in a high-pressure autoclave with an integrated optical path and a magnetic stirrer, fitted directly into a commercial spectrophotometer. The relative amount of lapachol extracted by supercritical CO2 at 40°C and 200 bar was ab…

Organic residues in lake and drinking water from the lagoa de Juturnaíba (região dos lagos - RJ, Brazil)

Various analytical methods for the determination of organic residues in water were applied to samples from the Lagoa de Juturnaíba in the Região dos Lagos, east of Rio de Janeiro. The concentrations of more than 60 pesticides and of different aminopolycarboxylic acids were determined using GC/MS detection, and a GC/MS screening procedure was applied to detect additional compounds. None of the investigated pesticide residues could be detected in the lake water at detection limits of less than 100 ng/L. EDTA was detected at a concentration level of 2 mg/L in the lake and in drinking water prepared from this lake. Traces of biphenyl were identified by GC/MS in the lake water, the source of whi…

Polar drug residues in sewage and natural waters in the state of Rio de Janeiro, Brazil

The drug residues of lipid regulators, anti-inflammatories and some drug metabolites have been detected in raw sewage, treated waste water and river water in the state of Rio de Janeiro, Brazil. These residues are mainly derived from humans via excretion. The median concentrations in the effluents of sewage treatment plants (STPs) of most drugs investigated in this study ranged from 0.1 to 1 microgram/l. The removal rates of individual drugs during passage through a Brazilian STP varied from 12 to 90%. As a consequence of the incomplete removal of these residues during passage through a STP, rivers were also found to be contaminated. Median concentrations ranged from between 0.02 and 0.04 m…

<title>Coumarin fluorescent probes by electro-optical and laser spectrofluorimetry methods</title>

Modified electro-optical absorption and emission methods were used to measure the dipole moments of six coumarin fluorescent probes (CU1, CU4, CU7, CU30, CU120, CU334) in the equilibrated ground, excited Franck-Condon and equilibrated excited states. The measurements were performed in cyclohexane and dioxane at room temperature. The equilibrated ground and excited states dipole measured by electro-optical methods are compared with those derived from other measurements techniques and from semiempirical calculations. Experiments and calculations performed in this work reveal a set of anomalous and interesting properties of CU7 and CU30 in solutions. The spectral dependence of some electro-opt…

Intramolecular Charge Transfer as Revealed by Results from the Measurement of Ground and Excited State Dipole Moments

Liquid chromatography detectors second, completely revised edition by R. P. W. Scott Perkin-Elmer Corporation, Instrument Group, Main Avenue, Norwalk, CT 06859-0089, USA Journal of Chromatography Library - Volume 33 1986 xvi + 272 pages Price: US $64.75 / Dfl. 175.00 ISBN 0-444-42610-8

Optische Detektoren in der Flüssigkeits-Chromatographie

Die durch physikalische Grunduberlegungen gegebene theoretische Grenze in der Nachweisempfindlichkeit optischer Detektoren fur die Flussigkeits-Chromatographie wird diskutiert, fur Photometer-, Fluorometer-, Refraktometer- und Polarimeterdetektoren berechnet und mit den heute erreichten Nachweisempfindlichkeiten verglichen.

Electric Field Dependence of the Fluorescence Intensity of Solute Molecules and Fourth Order Effects

Abstract The effect of an external electric field on the total fluorescence of solute molecules is studied up to fourth order theoretically, and is checked experimentally with 4´-N,N-dimethylamino- 4-nitrostilbene in dioxane at room temperature.

UV-Filtersubstanzen in Wasser und Fischen

Zur Erfassung der UV-Filtersubstanzen wird eine Methode vorgestellt, die die simultane Bestimmung dieser Verbindungen und von Organochlorverbindungen wie PCB und DDT in unterschiedlichen Fischkompartimenten bis in den ng/kg-Bereich ermoglicht. Die Nachweisgrenzen liegen zwischen 40 und 90 ng/kg Filet und die Wiederfindungsraten bewegen sich zwischen 78 und 104%. Die Belastung von Wasser und Fischen des Meerfelder Maares, Eifel, mit UV-Filtersubstanzen wurde 1991 und 1993 exemplarisch untersucht. Insgesamt konnten in den Fischen des Meerfelder Maares 6 UV-Filtersubstanzen identifiziert und quantifiziert werden. Die im Sommer 1991 gefangenen Barsche waren mit 2,0 mg/kg Fett (Summe nachgewiese…

Study of polychlorinated biphenyls in street dust by supercritical fluid extraction-gas chromatography/mass spectrometry

Street dust samples have been collected from highways, urban streets, a gasoline station, a pedestrian tunnel, and railway stations in some German cities. Nine polychlorinated biphenyls (PCBs from tri- to heptachlorobiphenyls) were quantitatively extracted by supercritical fluid extraction with CO2 at 200 bar and 40°C and analyzed by gas chromatography/mass spectrometry. The highest PCB loads (sum of the nine studied PCBs) of ca. 1 to 4 μg/g have been found in the samples from motorway A60 near Mainz, while in almost all other samples PCBs could be detected at only ca. 0.1 to 1 μg/g. At three sampling sites, a winter maximum of the PCB concentrations has been found.

Dipole moments of aminophthalimides determined by modified electro-optical absorption and emission measurements

Modified electro-optical absorption and emission methods were used to measure the electric dipole moments of five aminophthalimides in their ground and excited states. The equilibrated ground and excited state dipole moments measured by these methods are in reasonable agreement with those derived from other measurement techniques, confirming the general validity of these methods. A difference is observed between the properties of 3-aminophthalimide (3AP) and 4-amino-N-methylphthalimide (4ANMP) in different solvents. The equilibrated dipole moment of 3AP in its excited state is practically independent of the solvent polarity in contrast with 4ANMP. The possible mechanism of this effect is di…

Considerations on the dipole moment of molecules forming the twisted intramolecular charge transfer state

Several derivatives of dual-fluorescing dimethylaminobenzonitrile (DMABN) are compared regarding their ground and excited-state dipole moments extracted from electro-optical emission and solvatochromic measurements. The comparison includes bridged model compounds as well as compounds with different degrees of steric hindrance to planarity, as well as ester and carbazolyl derivatives. The results are discussed on the basis of the twisted intramolecular charge transfer (TICT) model, the most widely accepted model. They show that (i) the dipole moment of the A (TICT) state (long-wavelength band) shows only little solvent sensitivity (polarizability), (ii) this observed small dependence of the …

Site selectivity in excited-state intramolecular proton transfer in flavonols

Abstract To investigate 4′-(diethylamino) (FET) and 4′-N-(15-azacrown-5) (FCR) derivatives of 3-hydroxyflavone in binary solvents and erythrocyte ghosts, we used the red-edge excitation spectroscopy (REES). The results obtained prove the existence of spectral heterogeneity of flavonols in the studied systems. The effect manifests itself in the dependence of the efficiency of excited-state intramolecular proton transfer (ESIPT) on the excitation frequency. The electro-optical absorption method (EOAM) was used to measure the dipole moments of the normal form of FET. The electric dipole moments in the ground (μg) and excited Franck–Condon ( μ e FC ) states have the values 22.7×10−30 and 53.3×1…

Solubility of some pesticides in supercritical CO2

The solubility limits of some pesticides (Linuron, Methoxychlor, Diclofopmethyl, Diclofop and 2,4-D) and of 3,4-dichloroaniline have been determined in supercritical CO2 at 200 bar and 40° C, using the Milton Roy sample preparation accessory SPATM. Depending on the polarity and vapour pressure of the investigated compounds, the solubility was found to be between 0.3 and 12 gl−1.

Statistische Methoden für die Analytik Grundlagen und praktische Anwendungen

Im Laufe ihrer langen Geschichte hat die Chemie zum besseren Verstandnis und zur genaueren Beschreibung experimentell beobachteter Phanomene zunehmend kompliziertere mathematische Formalismen herangezogen und auch mitentwickelt — man denke zum Beispiel an Thermodynamik, die Kinetik und die Quantenchemie. Mit den Angaben von Mittelwerten und Standardabweichungen als Mittel etwa zur zusammenfassenden Angabe einer Reihe von Mesergebnissen hat sie auch Hilfsmittel der Statistik benutzt. Aber erst die Entwicklung der modernen analytischen Chemie zu einem betont quantitativen Zweig der Chemie, der obendrein uber die angewandten Nachweismethoden heute in hohem Mase physikalisch durchdrungen ist, h…

Influence of rotational diffusion on the electric field induced effect on the fluorescence spectrum of diluted solutions I. Theory and numerical simulations

Abstract The theory for the calculation of excited state dipole moments from electrooptical emission measurements, developed by Baumann and Deckers (Ber. Bunsenges. Phys. Chem. 81 (1977) 786) presupposes a Boltzmann distribution for the emitting molecules. Using the anisotropic rotational diffusion model and taking into account all important electric field induced effects, we derive equations that describe quantitatively the electric field effect on the fluorescence of an ensemble of solute rigid molecules which are not yet equilibrated with respect to their orientation when emitting. Numerical simulations are performed to compare the general case and the limiting case of a prevailing Boltz…

Electro-optical and laser spectrofluorimetry study of coumarins 7 and 30: evidence for the existence of the close-lying electronic states and conformers

Our experiments and calculations reveal a set of anomalous and interesting properties of coumarin 7 (CU7) and coumarin 30 (CU30) in solution. The spectral dependence of electro-optical coefficients and, consequently, dipole moments indicates that the absorption band is a superposition of several (at least two) electronic transitions. Probably, there are two close-lying π,π* singlet electronic excited states which contribute to the first absorption band. The calculations using the MM2 program show that both dyes in the ground state have two stable plane anti conformers. From time-resolved spectrofluorimetric measurements we obtained evidence for the existence of conformers in paraffin oil so…

New developments in immunochemical water analysis down to 30 mul sample volume.

Abstract The determination of trace levels of pesticides like atrazine in water samples of small, restricted volumes is one of the future demands of environmental analysis. In a brief review existing chromatographic and immunochemical methods for atrazine are critically discussed. Then a simple rapid enzyme-linked immunosorbent assay (ELISA) using the tip of an inoculation needle as a solid surface is presented. The sample volume could be reduced to 30 μl. The assay had a centre of the test IC50 of 0.12 μg l−1 and permitted the characterisation of atrazine at levels of 0.022–2.90 μg l−1. A first outlook for automatisation is given. The new method was compared with an ELISA using 96 well mic…

Contributions to the analysis of organic xenobiotics in fish

For the residue-analysis of fish samples, a method has been developed to separate the medium polar triazines and acetamides together with lipophilic xenobiotics (organochlorine pesticides, PCBs and octachlorostyrene) from fish tissue. The detection limits of the analytes are mostly within the ppt-range (ng/kg fillet) and vary between 40 and 1050 ng/kg fillet of fish. Their recoveries range from 75 to 108%, spiked at 1.5 μg/kg. The substances are extracted with a mixture of petroleum ether/ethylacetate (2:1) using a soxhlet apparatus. Subsequently, the lipids in the sample extracts are reduced to 0.4% by gel chromatography. A 5 g silica gel clean-up separates the analytes according to their …

Use of the red-edge excitation effect for investigation of dielectric interactions in biomembranes

Dipole moments of the fluorescent probes 1-phenylnaphthylamine (1-AN) and 1-anilinonaphthalene-8-sulfonate (1,8-ANS) are measured using electro-optical absorption and emission methods. Dipole moments in the ground and excited states were measured in cyclohexane and dioxane. It is shown that the charge distributions in the 1-AN and 1,8-ANS molecules differ substantially. The spectral dependence of the electro-optical coefficients suggests that the absorption spectrum of 1,8-ANS is due to a superposition of (at least two) electronic transitions. It is found that spectra of 1-AN in erythocyte ghosts are inhomogeneously broadened. The above effect makes it possible to selectively excite probe m…

Supercritical fluid extraction of pesticides

The extraction behaviour of 10 μg samples of five pesticides and some related compounds from glass wool with supercritical CO2 has been investigated under several conditions (10 MPa, 20 MPa extraction pressure, 313 K, dry and water saturated CO2). The extraction fluid was decompressed over a line of little columns, filled with 3μ Si60 or RP18, and the amount of deposited material was analyzed by HPLC for each of these columns. Due to the progressive pressure/density reduction along the line, the solubility diminishes and hence the compounds are deposited according to their polarity/vapor pressure earlier or later on the line. Thus extraction and prefractionation of compounds of different po…

Ground- and First-Excited-Singlet-State Electric Dipole Moments of Some Photochromic Spirobenzopyrans in Their Spiropyran and Merocyanine Form

The dipole moments of four photochromic derivatives of indolinospirobenzopyran have been studied in their spiro and their open merocyanine form, in dioxane. Determinations have been done by electrooptical absorption measurements (EOAM). To prepare either a pure spiropyran or a pure merocyanine form solution, the experimental setup had to be modified by addition of a second light beam. In this way thermal equilibration between the spiropyran and the merocyanine form and switching from one form to the other induced by the measuring light beam could be avoided. The ground-state dipole moment of the spiro form amounts to (10−15) × 10-30 C m and increases strongly to about 60 × 10-30 C m with th…

Ground and excited state dipole moments of coumarin laser dyes: Investigation by electro-optical absorption and emission methods

Abstract Modified electro-optical absorption and emission methods were used to measure the dipole moments of four efficient coumarin laser dyes (CU1, CU4, CU120, CU334) in the equilibrated ground, excited Franck-Condon and equilibrated excited states. The measurements were performed in cyclohexane (CU1, CU120, CU334) and dioxane (all CUs) at room temperature. Our results show that the charge distribution in CU4 differs substantially from that in the other CUs. The equilibrated ground and excited state dipole moments measured by electro-optical methods are compared with those derived from other measurement techniques and from semiempirical calculations. The possible role of twisted intermole…

Comparison of an indirect format ELISA on modified graphite and polystyrene surfaces against triazines.

An indirect format enzyme-linked immuno-sorbent assay (ELISA) on graphite rods (Ø 0.8 mm x 20 mm) and, for comparison, on microtiter plates has been developed against terbuthylazine. For this purpose, a series of 2-aminoalkyl-4-chloro-6-terbuthyl-s-triazine-2,6- diamine ELISA haptens with alkyl spacer lengths of 2, 4, 6, and 8 CH2 groups has been synthesized. The graphite rods or the microtiter plates were covered by a polymerized glutaraldehyde network, and the ELISA haptens have been coupled by imino coupling to the free aldehyde groups of that network. ε-Aminocaproic acid has been used as an agent to block unspecific binding sites. The ELISA was run in a competitive mode, where the immob…

Oligo(phenylenvinylene) mit terminaler Donor-Acceptor-Substitution

Elektrooptische Emissionsuntersuchungen, III. Das Dipolmoment von trans-p-Dimethylamino-p′-nitrostilben im ersten angeregten Singulettzustand

Aus elektrooptischen Emissions- und Absorptionsuntersuchungen in flussigen und glasig erstarrten Losungen kombiniert mit dielektrischen Untersuchungen konnten u. a. das Dipolmoment und die Polarisierbarkeitskomponente in Richtung des Dipolmoments von trans-p-Dimethylamino-p′-nitrostilben (DMANS) im ersten angeregten Singulettzustand bestimmt werden zu μ0a = (63 ± 5) · 10−30 Cm und α0az = (442 ± 65) · 10−40 CV−1 m2. Es zeigte sich, das die elektrooptischen Absorptions- und Emissionsuntersuchungen an DMANS in unpolaren Losungen zu einem konsistenten Satz von Dipolmomenten fuhren, das also die Aquilibrierung mit der Umgebung nach Anre-gung im unpolaren Cyclohexan keinen Einflus auf das permane…

Direct potentiometric immunoelectrodes

TK pencil fine mines type Faber Castell Super polymer from Staedtler are used as graphite based material for an atrazine-sensitive immunoelectrode. Eighteen procedures are tested to immobilize antibodies against atrazine but only one turned out to be useful for the preparation of a graphite based immunoelectrode. It incorporates binding of glutardialdehyde to active sites of the graphite surface and subsequent cross-linking of the antibodies with glutardialdehyde. The method has been carefully optimized with respect to selectivity and the cross-sensitivity is determined for such an electrode based on atrazine-rabbit and atrazine-sheep antibodies as well. Due to the structural difference of …

Elektrooptische Emissionsmessungen, II. Eine Apparatur zur spektralen Untersuchung feldinduzierter Änderungen der Fluoreszenzintensität von Molekülen in Lösungen

Es wird ein Spektralfluorometer beschrieben und diskutiert, das es gestattet, die Abhangigkeit der Fluoreszenzintensitat von einem auseren elektrischen Feld zu messen. Die experimentellen Variablen sind dabei die Anregungs- und Emissionswellenzahl sowie die Polarisationsrichtung des Anregungs- und Emissionslichts. A spectrofluorometer is described and discussed, which provides the possibility of measuring the dependence of the fluorescence on an external electric field. The experimentally variable parameters are the wavenumber and the direction of the polarization of the exciting and emitted light.

Incomplete degradation of linear alkylbenzene sulfonate surfactants in Brazilian surface waters and pursuit of their polar metabolites in drinking waters.

In Brazil more than 90% of the population are not connected to municipal wastewater treatment plants. As a consequence, surface waters receive continuously considerable amounts of untreated domestic sewage containing surfactants as a major constituent. Such polluted waters gave rise to special interest if they are used as a source for the production of drinking water. In this work, the river Rio Macacu (State Rio de Janeiro, Brazil) was monitored for the occurrence of the most widely used anionic surfactant linear alkylbenzene sulfonate (LAS) together with its main degradative product, sulfophenyl carboxylates (SPC). In order to pursue the fate of both compounds after emission into the rive…

Dipole Moments and the Direction of the Transition Dipole Moment of Some Intramolecular Exciplexes

The dipole moments of some intramolecular exciplex systems have been determined from the effect of an electric field on their fluorescence and are compared to those estimated from solvent shift measurements. The charge transfer between the donor and acceptor subunits is between 0.6 and 0.9 of a full charge transfer. The face-to-face type exciplexes show considerable deviations from the general behaviour what might be due to some admixture of locally excited configurations to the exciplex wave function, in this way reducing the dipole moment values and changing the direction of the transition dipole moment.

Pigments and their solubility in and extractability by supercritical CO2 - I: the case of curcumin

A specially designed high-pressure cell was used simultaneously as extractor/autoclave and photometric cell in a Perkin Elmer Lambda 5 spectrophotometer. Based on this cell, a simple method was developed to determine the extractability of pigments by pure and by modified supercritical (sc) CO2. The method is demonstrated with curcumin from turmeric. With sc CO2 modified by 10% ethanol, the extraction yield for curcumin from two commercial finely ground dry turmeric samples was about 100%, measured by reference to the (complete) extraction of samples of the same charge with pure ethanol under standard conditions. Extractable curcumin content was from 1.8 to 2.5%, with three samples of turmer…

Chromatography with dense gases

A capillary restrictor for supercritical fluid chromatography (SFC) with CO2 was made by using a micro torch and fine emery cloths or grinding blocks. This restrictor could be drawn out either directly from the end of the analytical capillary column, or from a short piece of any capillary, which was then connected to the analytical column by standard techniques. It was found that the base current of a flame ionisation detector (FID) depends strongly on the position of the capillary end with respect to the FID flame tip and on the CO2 grade, of course. Best results have been achieved at around 5 to 7 mm distance between the restrictor and the flame tip ends, and using SFC grade CO2.

Selective gas chromatographic detectors by M. Dressler, Journal of Chromatography Library, 36, Elsevier Science Publishers, Amsterdam, 334 pages, 1986, Dfl. 195.00, ISBN 0-444-42488-1

Elektrooptische Emissionsmessungen, I. Der Einfluß eines äußeren elektrischen Feldes auf den von Molekülen in Lösungen emittierten Photonenstrom

Es wird der Einflus eines auseren elektrischen Feldes auf den von angeregten Molekulen in Losungen emittierten Photonenstrom untersucht. Es zeigt sich, das fur den Fall genugend langer Lebensdauer der Molekule im emissionsfahigen Zustand eine auswertbare Beziehung zwischen elektrischen Momenten der gelosten Molekule und der Anderung des emittierten Photonenstroms mit Anlegen eines auseren elektrischen Feldes besteht. The intensity of light emitted from excited molecules in solution depends on an external electric field. Assuming the lifetime of the solute molecules being long enough, an equation is derived that connects the change of the intensity of the emitted light to electric moments of…