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- Activated ester (2)
- Bifunctional (2)
- Biphenyl (2)
- CCQM (2)
- Conducting polyalkylthiophene (2)
- Electropolymerization (2)
- Fluorescent probe (2)
- Guided wave (2)
- Metrology (2)
- Photophysics (2)
Organisationseinheit der BAM
- 1 Analytische Chemie; Referenzmaterialien (8)
- 6 Materialchemie (7)
- 7 Bauwerkssicherheit (5)
- 1.7 Organische Spuren- und Lebensmittelanalytik (3)
- 6.3 Strukturanalytik (3)
- 1.2 Biophotonik (2)
- 1.8 Umweltanalytik (2)
- 3 Gefahrgutumschließungen; Energiespeicher (2)
- 3.1 Sicherheit von Gefahrgutverpackungen und Batterien (2)
- 6.1 Oberflächen- und Dünnschichtanalyse (2)
Three new thiophene derivatives containing different activated ester groups covalently attached to the thiophene ring via a linear undecyl spacer have been synthesized. Electropolymerization of these monomers in acetonitrile led to stable electroactive polymers, while activated functional groups withstand the polymerization conditions and were correctly incorporated in the resulting polymers. These polymers show the characteristic electrochemical behavior of poly(3-alkylthiophene)s with the reversible redox transition in the range of 0.70.9 V. UV/Vis spectra of them exhibit an absorption maximum at around 460 nm. Conductivity measurements on oxidized films of these polymers by means of the two-probe method gave values in the range of 10-310-2 S cm-1. The reactivity of the pendant activated ester groups was demonstrated by the reaction with butylamine, (4-amino-2-oxabutyl) ferrocene and 2-aminoanthraquinone. Spectroscopic studies and electrochemical characterization confirmed that the immobilized amino compounds are covalently bound to the polymer surfaces. These results suggest that the obtained new polymers can be used as electrically conducting carrier materials for the immobilization of biochemically interesting molecules.
1-Methyl-2-[4-phenyl-6-(pyridinium-2-yl)pyridin-2-yl]pyridinium diperchlorate, C22H19N32+·2ClO4-, (I), and 2-[4-(methoxyphenyl)-2,2'-bipyridin-6-yl]-1-methylpyridinium iodide, C23H20N3O+·I-, (II), both crystallize in the monoclinic space group P21/c. In contrast with the monocharged molecule of (II), the doubly charged molecule of (I) contains an additional protonated pyridine ring. One of the two perchlorate counter-anions of (I) interacts with the cation of (I) via an NHO hydrogen bond. In (II), two molecules related by a centre of symmetry are connected by weak ?? interactions, forming dimers in the crystal structure.
Based on donor (D)-acceptor (A) biphenyl (b) type molecules, a family of fluorescent reporters with integrated acceptor receptors and noncoordinating and coordinating donor substituents of varying strength has been designed for ratiometric emission sensing and multimodal signaling of metal ions and protons. In part 2 of this series on such charge transfer (CT) operated mono- and bifunctional fluorescent devices, the cation coordination behavior of the sensor molecules bpb-R equipped with a proton- and cation-responsive 2,2':6',2' '-terpyridine (bp) acceptor and either amino-type donor receptors (R = DMA, A15C5 = monoaza-15-crown-5) or nonbinding substituents (R = CF3, H, OMe) is investigated employing the representative metal ions Na(I), Ca(II), Zn(II), Hg(II), and Cu(II) and steady-state and time-resolved fluorometry. The bpb-R molecules, the spectroscopic behavior and protonation behavior of which have been detailed in part 1 of this series, present rare examples for CT-operated bifunctional fluorescent probes that can undergo consecutive and/or simultaneous analyte recognition. The analyte-mediated change of the probes' intramolecular CT processes yields complexation site- and analyte-specific outputs, i.e., absorption and fluorescence modulations in energy, intensity, and lifetime. As revealed by the photophysical studies of the cation complexes of these fluoroionophores and the comparison to other neutral and charged D-A biphenyls, the spectroscopic properties of the acceptor chelates of bpb-R and A- and D-coordinated bpb-R are governed by CT control of an excited-state barrier toward formation of a forbidden charge transfer state, by the switching between analytically favorable anti-energy and common energy gap law type behavior, and by the electronic nature of the ligated metal ion. This accounts for the astonishingly high fluorescence quantum yields of the acceptor chelates of bpb-R equipped with weak or medium-sized donors and the red emission of D- and A-coordinated bpb-R observed for nonquenching metal ions.
On the basis of biphenyl (b) type molecules bpb-R substituted with a 2,2':6',2' '-terpyridine acceptor (bp) and either amino-type donor receptors (R = dimethylamino (DMA), A15C5 = monoaza-15-crown-5) or nonbinding substituents (R = CF3, H, OMe) of various donor strengths, we developed a family of charge transfer (CT) operated monofunctional and bifunctional fluorescent sensors for protons and metal ions. These molecules are designed to communicate the interaction of an analyte with the acceptor and the donor receptor differing in basicity and cation selectivity by clearly distinguishable spectral shifts and intensity modulations in absorption and in emission as well as in fluorescence lifetime. From the dependence of the fluorescence spectra, fluorescence quantum yields, and fluorescence lifetimes of bpb-R on solvent polarity and proton concentration, the photophysics of bpb-R and their protonated analogues can be shown to be governed by the relaxation to a CT state of forbidden nature and by the switching between anti-energy and energy gap law type behaviors. This provides the basis for analytically favorable red shifted emission spectra in combination with comparatively high fluorescence quantum yields. Accordingly, bpb-H and bpb-OMe are capable of ratiometric emission signaling of protons. bpb-DMA reveals a protonation-induced ON-OFF-ON switching of its emission.
Taking into account the structural requirements for TICT-type sensor molecules, a general synthetic
route to derive pH and cation-responsive pretwisted donor (D)donor (D) biphenyls (b) equipped with
donor receptors is developed and a first model compound containing a mono aza-15-crown-5 and a
DMA receptor is synthesized, see Scheme 1. The spectroscopic properties of this new bifunctional
DD biphenyl are studied in the non-polar and polar solvents cyclohexane, acetonitrile, and methanol.
Protonation as well as complexation studies are performed with the representative metal ions Na(I),
K(I), Ca(II), Ag(I), Zn(II), Cd(II), Hg(II), and Pb(II) to reveal the potential of this molecule for
communication of whether none, only one, or both binding sites are engaged in analyte coordination
by spectroscopically distinguishable outputs. The results are compared to those obtained with closely
related donor (D)acceptor (A) substituted biphenyl-type sensor molecules and are discussed within
the framework of neutral and ionic D A biphenyls.
A systematic structural investigation of R-phenyl-substituted 2,2':6',2"-terpyridines, a family of mono- and bifunctional charge transfer (CT)-operated fluorescent reporters for protons and metal ions, is presented. These molecules are equipped with non-binding and analyte coordinating donor substituents R (R = CF3, H, OMe, OH, DMA, A15C5 equaling monoaza-15-crown-5) of various donor strength and display CT-controlled spectroscopic properties and communication of analytereceptor interactions. The crystal structures of the neutral fluorescent probes are compared to the structures of their terpyridine-alkylated or -protonated counterparts that represent model systems for acceptor protonation or cation coordination. The aim is here a better understanding of the complexation-induced structural and spectroscopic changes and the identification of common packing motifs of bpb-R thereby taking into account the importance of terpyridine building blocks for the construction of supramolecular systems and coordination arrays revealing ππ interactions.
Pyrrolovesamicols - synthesis, structure and VAChT binding of two 4-fluorobenzoyl regioisomers
(2012)
This Letter describes the synthesis of two regioisomers of a new class of vesamicol analogs as possible
ligands for imaging the vesicular acetylcholine transporter in future PET studies. The two pyrrolovesamicols
(±)-6a and (±)-6b were synthesized by nucleophilic ring opening reaction of a tetrahydroindole epoxide
precursor with 4-phenylpiperidine. The reaction mechanism of the synthesis was studied by HPLC
and the molecular structures were determined by X-ray structure analysis. Unexpected low binding affinities
to VAChT (Κi = 312 ± 73 nM for (±)-6a and Κi = 7320 ± 1840 nM for (±)-6b) were determined by competitive
binding analysis using a cell line stably transfected with ratVAChT and (–)-[3H]vesamicol.
Under the auspices of the Organic Analysis Working Group (OAWG) of the Comité Consultatif pour la Quantité de Matière (CCQM) a key comparison, CCQM K55.b, was coordinated by the Bureau International des Poids et Mesures (BIPM) in 2010/2011. Nineteen national measurement institutes and the BIPM participated. Participants were required to assign the mass fraction of aldrin present as the main component in the comparison sample for CCQM-K55.b which consisted of technical grade aldrin obtained from the National Measurement Institute Australia that had been subject to serial recrystallization and drying prior to sub-division into the units supplied for the comparison.
Aldrin was selected to be representative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molar mass range 300 Da to 500 Da] and low polarity (pKOW < -2) for which related structure impurities can be quantified by capillary gas phase chromatography (GC).
The key comparison reference value (KCRV) for the aldrin content of the material was 950.8 mg/g with a combined standard uncertainty of 0.85 mg/g. The KCRV was assigned by combination of KCRVs assigned by consensus from participant results for each orthogonal impurity class. The relative expanded uncertainties reported by laboratories having results consistent with the KCRV ranged from 0.3% to 0.6% using a mass balance approach and 0.5% to 1% using a qNMR method.
The major analytical challenge posed by the material proved to be the detection and quantification of a significant amount of oligomeric organic material within the sample and most participants relying on a mass balance approach displayed a positive bias relative to the KCRV (overestimation of aldrin content) in excess of 10 mg/g due to not having adequate procedures in place to detect and quantify the non-volatile content–specifically the non-volatile organics content–of the comparison sample.
There was in general excellent agreement between participants in the identification and the quantification of the total and individual related structure impurities, water content and the residual solvent content of the sample.
The comparison demonstrated the utility of 1H NMR as an independent method for quantitative analysis of high purity compounds. In discussion of the participant results it was noted that while several had access to qNMR estimates for the aldrin content that were inconsistent with their mass balance determination they decided to accept the mass balance result and assumed a hidden bias in their NMR data. By contrast, laboratories that placed greater confidence in their qNMR result were able to resolve the discrepancy through additional studies that provided evidence of the presence of non-volatile organic impurity at the requisite level to bring their mass balance and qNMR estimates into agreement.
Timber poles are commonly used for telecommunication and power distribution networks, wharves or jetties, piling or as a substructure of short span bridges. Most of the available techniques currently used for non-destructive testing (NDT) of timber structures are based on one-dimensional wave theory. If it is essential to detect small sized damage, it becomes necessary to consider guided wave (GW) propagation as the behaviour of different propagating modes cannot be represented by one-dimensional approximations. However, due to the orthotropic material properties of timber, the modelling of guided waves can be complex. No analytical solution can be found for plotting dispersion curves for orthotropic thick cylindrical waveguides even though very few literatures can be found on the theory of GW for anisotropic cylindrical waveguide. In addition, purely numerical approaches are available for solving these curves. In this paper, dispersion curves for orthotropic cylinders are computed using the scaled boundary finite element method (SBFEM) and compared with an isotropic material model to indicate the importance of considering timber as an anisotropic material. Moreover, some simplification is made on orthotropic behaviour of timber to make it transversely isotropic due to the fact that, analytical approaches for transversely isotropic cylinder are widely available in the literature. Also, the applicability of considering timber as a transversely isotropic material is discussed. As an orthotropic material, most material testing results of timber found in the literature include 9 elastic constants (three elastic moduli and six Poisson's ratios), hence it is essential to select the appropriate material properties for transversely isotropic material which includes only 5 elastic constants. Therefore, comparison between orthotropic and transversely isotropic material model is also presented in this article to reveal the effect of elastic moduli and Poisson's ratios on dispersion curves. Based on this study, some suggestions are proposed on selecting the parameters from an orthotropic model to transversely isotropic condition.
The requirement for a metrological infrastructure to ensure the interchangability of 'nonconventional’ energy gases within existing European infrastructure1 was the driving force behind the work undertaken in the three-year EMRP Characterisation of energy gases project EMRP ENG01 (June 2010 - May 2013).
As part of work package one of the project, Standards and methods were used to perform composition and impurity measurements on samples of real energy gases collected from around Europe. The aim of this study was to compare the results obtained from different labs, and thereby provide an evaluation of the labs’ capabilities and provide insight into the feasibility of different analytical methodologies for use with future measurements.
This paper presents the state-of-the-art of using non-destructive testing (NDT) methods based on elastic waves for the condition assessment of structural timber. Two very promising approaches based on the propagation and reflections of elastic waves are described. While the first approach uses ultrasonic echoes for the testing of wooden building elements, the second approach uses guided waves (GW) for the testing of timber pole and pile structures. The basic principle behind both approaches is that elastic waves induced in a timber structure will propagate through its material until they encounter a change in stiffness, cross-sectional area or density, at which point they will reflect back. By measuring the wave echoes, it is possible to determine geometric properties of the tested structures such as the back wall of timber elements or the underground length of timber poles or piles. In addition, the internal state of the tested structures can be assessed since damage and defects such as rot, fungi or termite attacks will cause early reflections of the elastic waves as well as it can result in changes in wave velocity, wave attenuation and wave mode conversion. In the paper, the principles and theory of using elastic wave propagation for the assessment of wooden building elements and timber pole/pile structures are described. The state-of-the-art in testing equipment and procedures is presented and detailed examples are given on the practical application of both testing approaches. Recent encouraging developments of cutting edge research are presented along with challenges for future research.
Porous Si3N4/SiC ceramics were prepared with Si and SiC as raw materials, Y2O3 as sintering additive and ZrO2 as nitrided catalyst through a rapid nitration process. The nitriding rate as a function of temperature and duration was investigated. The porous Si3N4/SiC ceramics with 8 wt% monoclinic ZrO2 addition that was nitrided at 1400 °C for 2 h exhibited the highest nitridation degree of 95%. The experimental results also demonstrated that the reciprocal formation of ZrO2 and ZrN can effectively enhance the level of nitridation by suppressing the melting of silicon in micro-regions. The effects of nitriding time on the mechanical properties of the specimens with ZrO2 as a catalyst was also studied. After nitrided at 1400 °C for various durations from 2 to 8 h, the porous Si3N4/SiC ceramics with the properties of a porosity over 39.8%, a flexural strength over 88.9 MPa and a linear shrinkage lower than 0.6% were achieved. The systematic investigation reveals the catalytic mechanism of ZrO2 in the synthesis of Si3N4/SiC ceramics.
This paper addresses operational modal analysis (OMA) and continuous dynamic monitoring (CDM) of two bridges. One of them is installed with Tuned Mass Dampers (TMDs) while another one is a normal bridge. Two ambient vibration tests were performed on these two bridges respectively. It is observed that not only installation of TMDs but also environmental factors influence the variations of structural frequencies, which may mask the subtle change induced by small structural changes. As a result, continuous dynamic monitoring systems were implemented on these two bridges, in order to evaluate efficiency of the TMD system, remove the environmental effects and build reliable damage indices that are only sensitive to structural changes. The results of CDM of these two bridges during several years are presented. Software systems developed for OMA and CDM are also introduced.
Under the Comité Consultatif pour la Quantité de Matière (CCQM), a key comparison, CCQM-K104, was coordinated by the National Institute of Metrology (NIM). The comparison was designed to demonstrate a laboratory's performance in determining the mass fraction of the main component in a complex high purity organic material. Nine NMIs or DIs participated in the comparison. Eight participants reported their results. An additional impurity was resolved from the avermectin B1a peak and was tentatively identified as an unknown impurity by NMIA (National Measurement Institute (Australia)). It was subsequently identified by NIM as a diastereoisomer of avermectin B1a at the C-26 position. Final reference value (KCRV) = 924.63 mg/g, with uncertainty (k=1) = 3.89 mg/g, and expanded uncertainty = 8.97 mg/g. The degrees of equivalence with the avermectin B1a KCRV for each participant were reported. The measurement results and degrees of equivalence should be indicative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of high structural complexity (relative molecular mass range of 500 Da -1000 Da and low polarity (-log KOW ≤ -2).
This paper presents a novel non-destructive testing and health monitoring system using a network of tactile transducers and accelerometers for the condition assessment and damage classification of foundation piles and utility poles. While in traditional pile integrity testing an impact hammer with broadband frequency excitation is typically used, the proposed testing system utilizes an innovative excitation system based on a network of tactile transducers to induce controlled narrow-band frequency stress waves. Thereby, the simultaneous excitation of multiple stress wave types and modes is avoided (or at least reduced), and targeted wave forms can be generated. The new testing system enables the testing and monitoring of foundation piles and utility poles where the top is inaccessible, making the new testing system suitable, for example, for the condition assessment of pile structures with obstructed heads and of poles with live wires. For system validation, the new system was experimentally tested on nine timber and concrete poles that were inflicted with several types of damage. The tactile transducers were excited with continuous sine wave signals of 1 kHz frequency. Support vector machines were employed together with advanced signal processing algorithms to distinguish recorded stress wave signals from pole structures with different types of damage. The results show that using fast Fourier transform signals, combined with principal component analysis as the input feature vector for support vector machine (SVM) classifiers with different kernel functions, can achieve damage classification with accuracies of 92.5% ± 7.5%.
The comparison required the assignment of the mass fraction of folic acid present as the main component in the comparison sample. Performance in the comparison is representative of a laboratory's measurement capability for the purity assignment of organic compounds of medium structural complexity [molecular weight range 300–500] and high polarity (pKOW < −2).
Methods used by the eighteen participating NMIs or DIs were based on a mass balance (summation of impurities) or qNMR approach, or the combination of data obtained using both methods. The qNMR results tended to give slightly lower values for the content of folic acid, albeit with larger associated uncertainties, compared with the results obtained by mass balance procedures. Possible reasons for this divergence are discussed in the report, without reaching a definitive conclusion as to their origin.
The comparison demonstrates that for a structurally complex polar organic compound containing a high water content and presenting a number of additional analytical challenges, the assignment of the mass fraction content property value of the main component can reasonably be achieved with an associated relative standard uncertainty in the assigned value of 0.5%