TY - JOUR A1 - Schwarze, Thomas A1 - Dosche, Carsten A1 - Flehr, Roman A1 - Klamroth, Tillmann A1 - Löhmannsröben, Hans-Gerd A1 - Saalfrank, Peter A1 - Cleve, Ernst A1 - Buschmann, Hans-Jürgen A1 - Holdt, Hans-Jürgen T1 - Combination of a CT modulated PET and an intramolecular excimer formation to quantify PdCl2 by large fluorescence enhancement N2 - The [6.6](9,10)anthracenophane 1 (Scheme 1) is a selective fluoroionophore for the detection of PdCl2 with a large fluorescence enhancement factor (I/I-0 > 250). Y1 - 2010 UR - http://pubs.rsc.org/en/content/articlehtml/2010/cc/b919973j U6 - https://doi.org/10.1039/B919973j SN - 1359-7345 ER - TY - JOUR A1 - Schwarze, Thomas A1 - Dosche, Carsten A1 - Flehr, Roman A1 - Klamroth, Tillmann A1 - Löhmannsröben, Hans-Gerd A1 - Saalfrank, Peter A1 - Cleve, Ernst A1 - Buschmann, Hans-Jürgen A1 - Holdt, Hans-Jürgen T1 - Combination of a CT modulated PET and an intramolecular excimer formation to quantify PdCl2 by large fluorescence enhancement Y1 - 2010 UR - http://www.rsc.org/ej/CC/2010/b919973j.pdf SN - 1359-7345 ER - TY - GEN A1 - Schwarze, Thomas A1 - Riemer, Janine A1 - Müller, Holger A1 - John, Leonard A1 - Holdt, Hans‐Jürgen A1 - Wessig, Pablo T1 - Na+ Selective Fluorescent Tools Based on Fluorescence Intensity Enhancements, Lifetime Changes, and on a Ratiometric Response T2 - Postprints der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - Over the years, we developed highly selective fluorescent probes for K+ in water, which show K+-induced fluorescence intensity enhancements, lifetime changes, or a ratiometric behavior at two emission wavelengths (cf. Scheme 1, K1-K4). In this paper, we introduce selective fluorescent probes for Na+ in water, which also show Na+ induced signal changes, which are analyzed by diverse fluorescence techniques. Initially, we synthesized the fluorescent probes 2, 4, 5, 6 and 10 for a fluorescence analysis by intensity enhancements at one wavelength by varying the Na+ responsive ionophore unit and the fluorophore moiety to adjust different K-d values for an intra- or extracellular Na+ analysis. Thus, we found that 2, 4 and 5 are Na+ selective fluorescent tools, which are able to measure physiologically important Na+ levels at wavelengths higher than 500 nm. Secondly, we developed the fluorescent probes 7 and 8 to analyze precise Na+ levels by fluorescence lifetime changes. Herein, only 8 (K-d=106 mm) is a capable fluorescent tool to measure Na+ levels in blood samples by lifetime changes. Finally, the fluorescent probe 9 was designed to show a Na+ induced ratiometric fluorescence behavior at two emission wavelengths. As desired, 9 (K-d=78 mm) showed a ratiometric fluorescence response towards Na+ ions and is a suitable tool to measure physiologically relevant Na+ levels by the intensity change of two emission wavelengths at 404 nm and 492 nm. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1136 KW - crown compounds KW - fluorescence lifetime KW - fluorescent probes KW - ratiometric KW - sodium Y1 - 2021 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-437482 SN - 1866-8372 IS - 1136 ER - TY - JOUR A1 - Schwarze, Thomas A1 - Mueller, Holger A1 - Schmidt, Darya A1 - Riemer, Janine A1 - Holdt, Hans-Jürgen T1 - Design of Na+-Selective Fluorescent Probes: A Systematic Study of the Na+-Complex Stability and the Na+/K+ Selectivity in Acetonitrile and Water JF - Chemistry - a European journal N2 - There is a tremendous demand for highly Na+-selective fluoroionophores to monitor the top analyte Na+ in life science. Here, we report a systematic route to develop highly Na+/K+ selective fluorescent probes. Thus, we synthesized a set of fluoroionophores 1, 3, 4, 5, 8 and 9 (see Scheme 1) to investigate the Na+/K+ selectivity and Na(+-)complex stability in CH3CN and H2O. These Na+-probes bear different 15-crown-5 moieties to bind Na+ stronger than K+. In the set of the diethylaminocoumarin-substituted fluoroionophores 1-5, the following trend of fluorescence quenching 1 > 3 > 2 > 4 > 5 in CH3CN was observed. Therefore, the flexibility of the aza-15-crown-5 moieties in 1-4 determines the conjugation of the nitrogen lone pair with the aromatic ring. As a consequence, 1 showed in CH3CN the highest Na+-induced fluorescence enhancement (FE) by a factor of 46.5 and a weaker K+ induced FE of 3.7. The Na+-complex stability of 1-4 in CH3CN is enhanced in the following order of 2 > 4 > 3 > 1, assuming that the O-atom of the methoxy group in the ortho-position, as shown in 2, strengthened the Na+-complex formation. Furthermore, we found for the N( o-methoxyphenyl) aza-15-crown-5 substituted fluoroionophores 2, 8 and 9 in H2O, an enhanced Na+-complex stability in the following order 8 > 2 > 9 and an increased Na+/K+ selectivity in the reverse order 9 > 2 > 8. Notably, the Na+-induced FE of 8 (FEF = 10.9), 2 (FEF = 5.0) and 9 (FEF = 2.0) showed a similar trend associated with a decreased K+-induced FE [8 (FEF = 2.7) > 2 (FEF = 1.5) > 9 (FEF = 1.1)]. Here, the Na+-complex stability and Na+/K+ selectivity is also influenced by the fluorophore moiety. Thus, fluorescent probe 8 (K-d = 48 mm) allows high-contrast, sensitive, and selective Na+ measurements over extracellular K+ levels. A higher Na+/K+ selectivity showed fluorescent probe 9, but also a higher Kd value of 223 mm. Therefore, 9 is a suitable tool to measure Na+ concentrations up to 300 mm at a fluorescence emission of 614 nm. KW - crown compounds KW - fluorescence KW - fluorescent probes KW - potassium KW - sodium Y1 - 2017 U6 - https://doi.org/10.1002/chem.201605986 SN - 0947-6539 SN - 1521-3765 VL - 23 SP - 7255 EP - 7263 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Schwarze, Thomas A1 - Müller, Holger A1 - Ast, Sandra A1 - Steinbrück, Dörte A1 - Eidner, Sascha A1 - Geißler, Felix A1 - Kumke, Michael Uwe A1 - Holdt, Hans-Jürgen ED - Kumke, Michael Uwe T1 - Fluorescence lifetime-based sensing of sodium by an optode JF - Chemical Communications N2 - We report a 1,2,3-triazol fluoroionophore for detecting Na+ that shows in vitro enhancement in the Na+-induced fluorescence intensity and decay time. The Na+-selective molecule 1 was incorporated into a hydrogel as a part of a fiber optical sensor. This sensor allows the direct determination of Na+ in the range of 1–10 mM by measuring reversible fluorescence decay time changes. KW - ion optodes KW - sensors KW - indicators KW - chromoionophore KW - ionophore KW - membrane KW - switches KW - systems KW - samples KW - green Y1 - 2014 SN - 0022-4936 SN - 0009-241X SP - 14167 EP - 14170 PB - The Royal Society Chemistry CY - Cambridge ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Mickler, Wulfhard A1 - Kelling, Alexandra A1 - Schilde, Uwe A1 - Krüger, Hans-Joerg A1 - Holdt, Hans-Jürgen T1 - Mono- and dinuclear Ruthenium(II)-1,6,7,12-Tetraazaperylene complexes of N,N '-Dimethyl-2,11-diaza[3.3](2,6)-pyridinophane JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - Ruthenium(II) complexes [Ru(L-N4Me2)(dape)](PF6)2 {[1](PF6)2}, [Ru(L-N4Me2)(tape)](PF6)2 {[2](PF6)2}, and [{Ru(L-N4Me2)}2(mu-tape)](PF6)4 {[3](PF6)4} were synthesized in two reaction steps by first reacting [Ru(DMSO)4Cl2] with tetraazamacrocyclic ligand N,N'-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) in ethanol under microwave irradiation to the intermediate [Ru(L-N4Me2)Cl2], which was subsequently, without further isolation, reacted with 1,12-diazaperylene (dape) or 1,6,7,12-tetraazaperylene (tape). X-ray structures of [Ru(L-N4Me2)(dape)](PF6)2, [Ru(L-N4Me2)(tape)](PF6)2.acetone, and [{Ru(L-N4Me2)}2(mu-tape)](ClO4)4.MeCN were determined. The UV/Vis absorption spectra of [1](PF6)2, [2](PF6)2, and [3](PF6)4 in acetonitrile display intense low-energy dp(Ru)?p* (dape or tape) MLCT absorption bands centered at 579, 637, and 794 nm, respectively. Reversible metal oxidations for the bimetallic complex [{Ru(L-N4Me2)}2(mu-tape)]4+ ([3]4+) are detected at 1.69 and 1.28 V vs. SCE. The potential difference ?E = 410 mV and the intervalence-charge-transfer (IVCT) transition at 2472 nm indicate a high degree of electronic interaction between the two ruthenium ions mediated through the tape bridging ligand. All three complexes, [1]2+, [2]2+, and [3]4+, were characterized by UV/Vis spectroelectrochemistry. The monooxidized and monoreduced states, [1]3+, [2]3+, [3]5+, and [1]+, [2]+, [3]3+, are accessible by reversible one-electron oxidation and one-electron reduction processes, respectively, as documented by the observation of several stable isosbestic points in the spectral progressions. The second reduction in each complex and the second oxidation in [3]4+ prove to be irreversible in these spectroelectrochemical experiments. Monoreduced species [1]+, [2]+, and [3]3+ yield EPR signals indicating that the unpaired electron is mainly centered on the large surface ligands dape or tape. KW - Ruthenium KW - Macrocyclic li-gands KW - N ligands KW - Redox chemistry KW - Mixed-valent compounds Y1 - 2012 U6 - https://doi.org/10.1002/ejic.201200667 SN - 1434-1948 IS - 29 SP - 4632 EP - 4643 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Träger, Juliane A1 - König, Jana A1 - Städtke, Anja A1 - Holdt, Hans-Jürgen T1 - Development of a solvent extraction system with 1,2-bis(2-methoxyethylthio) benzene for the selective separation of palladium(II) from secondary raw materials JF - Hydrometallurgy : an international journal devoted to all aspects of the aqueous processing of metals N2 - The chelating dithioether 1,2-bis(2-methoxyethylthio)benzene. a novel solvent extractant for Pd(II), is aimed to be utilised in the selective recovery of palladium from spent automotive catalysts. For that, the extraction system has been further customised, including the choice of an appropriate diluent (1,2-dichlorobenzene) as well as an effective stripping agent (0.5 M thiourea in 0.1 M HCl), which both have been selected from a number of potential agents. It is shown in batch experiments that the selectivity for Pd(II) is maintained when the organic phase (10(-2) M 1,2-bis(2-methoxyethylthio)benzene in 1,2-dichlorobenzene) is used several times to extract an oxidising leach solution. According to the McCabe-Thiele plot two theoretical stages are needed to extract more than 98% of the Pd(II) contained in that solution. The calculation of the thermodynamic quantities Delta H degrees. Delta S degrees and Delta G degrees reveals that the reaction is entropy driven - the temperature has only a slight influence on the extraction yield. It is demonstrated that the mono-oxidised extractant has a catalytic effect on the extraction kinetics when the aqueous phase contains highly concentrated hydrochloric acid. HPLC measurements prove the presence of small quantities of 1-(2-methoxyethylsulfinyl)-2-(2-methoxyethylthio) benzene in the organic phase. KW - Solvent extraction KW - Palladium KW - S ligands KW - Extraction system development KW - Stripping Y1 - 2012 U6 - https://doi.org/10.1016/j.hydromet.2012.07.002 SN - 0304-386X SN - 1879-1158 VL - 127 IS - 5 SP - 30 EP - 38 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Brietzke, Thomas Martin A1 - Mickler, Wulfhard A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen T1 - Mono- and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - We report the synthesis of free 1,6,7,12-tetraazaperylene (tape). Tape was obtained from 1,1'-bis-2,7-naphthyridine by potassium promoted cyclization followed by oxidation with air. Mono-and dinuclear ruthenium(II) 1,6,7,12-tetraazaperylene complexes of the general formulas [Ru(L-L)(2)(tape)](PF6)(2), [1] (PF6)(2)-[5](PF6)(2), and [{Ru(L-L)(2)}(2)(mu-tape)](PF6)(4), [6](PF6)(4)-[10](PF6)(4), with{L-L = phen, bpy, dmbpy (4,4'-dimethyl-2,2'-bipyridine), dtbbpy (4,4'-ditertbutyl-2,2'-bipyridine) and tmbpy (4,4' 5,5'-tetramethyl-2,2'- bipyridine)}, respectively, were synthesized. The X-ray structures of tape center dot 2CHCl(3) and the mononuclear complexes [Ru(bpy)(2)(tape)](PF6)(2)center dot 0.5CH(3)CN center dot 0.5toluene, [Ru(dmbpy)(2)(tape)] (PF6)(2)center dot 2toluene and [Ru(dtbbpy)(2)(tape)](PF6)(2) center dot 3acetone center dot 0.5H(2)O were solved. The UV-vis absorption spectra and the electrochemical behavior of the ruthenium(II) tape complexes were explored and compared with the data of the analogous dibenzoeilatin (dbneil), 2,2'-bipyrimidine (bpym) and tetrapyrido [3,2-a:2',3'-c:3 '',2''-h:2''',3'''-j] phenazin (tpphz) species. Y1 - 2012 U6 - https://doi.org/10.1039/c2dt11805j SN - 1477-9226 VL - 41 IS - 9 SP - 2788 EP - 2797 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Träger, Juliane A1 - Klamroth, Tillmann A1 - Kelling, Alexandra A1 - Lubahn, Susanne A1 - Cleve, Ernst A1 - Mickler, Wulfhard A1 - Heydenreich, Matthias A1 - Müller, Holger A1 - Holdt, Hans-Jürgen T1 - Complexation of Palladium(II) with unsaturated Dithioethers a systematic development of highly selective ligands for solvent extraction JF - European journal of inorganic chemistry : a journal of ChemPubSoc Europe N2 - There is a demand for new and robust PdII extractants due to growing recycling rates. Chelating dithioethers are promising substances for solvent extraction as they form stable square-planar complexes with PdII. We have modified unsaturated dithioethers, which are known to coordinate PdII, and adapted them to the requirements of industrial practice. The ligands are analogues of 1,2-dithioethene with varying electron-withdrawing backbones and polar end-groups. The crystal structures of several ligands and their palladium complexes were determined as well as their electro- and photochemical properties, complex stability and behaviour in solution. Solvent extraction experiments showed the superiority of some of our ligands over conventionally used extractants in terms of their very fast reaction rates. With highly selective 1,2-bis(2-methoxyethylthio)benzene (4) it is possible to extract PdII from a highly acidic medium in the presence of other base and palladium-group metals. KW - Renewable resources KW - Palladium KW - Chelates KW - Ligand design KW - S li-gands Y1 - 2012 U6 - https://doi.org/10.1002/ejic.201101406 SN - 1434-1948 IS - 14 SP - 2341 EP - 2352 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Hahn, Simone A1 - Holdt, Hans-Jürgen T1 - Extraction of hexachloroplatinate from hydrochloric acid solutions with phosphorylated hexane-1,6-diyl polymers JF - Reactive & functional polymers N2 - A series of diols (diethylene glycol, triethylene glycol, butane-1,4-diol and hexane-1,6-diol) were immobilized onto Merrifield resin and subsequently phosphorylated with dialkyl chlorophosphate (alkyl = Me, Et, Bu). The resins bearing hexane-1,6-diyl groups exhibited very good extraction abilities in regard to precious metal chloro complexes like platinum(IV), palladium(II) and rhodium(III). In batch experiments, more than 98% of Pt(IV) is extracted even when the metal and the hydrochloric acid concentration is enhanced significantly. Elution can be achieved with a solution of 0.5 mol L-1 thiourea in 0.1 mol L-1 hydrochloric acid. In the presence of other noble metals, platinum(IV) is preferentially bound. The extraction yield decreases in slightly acidic solution in the following order: Pt(IV)approximate to Pd(II)>Rh(III) and changes with increasing hydrochloric acid concentration to Pt(IV)>Pd(II)>> Rh(III). At different ratios of metal and acid, the temperature has nearly no influence on the platinum extraction. On slightly acidic media, the extraction of rhodium decreases by 30% when the temperature is increased from 10 degrees C to 40 degrees C. When the acid and metal concentration is enhanced, the palladium extraction decreases by 7-9%, depending on the resin. KW - Solid-phase extraction KW - Platinum group metals KW - Modified polymer resin KW - Phosphate KW - Adsorption isotherm Y1 - 2012 U6 - https://doi.org/10.1016/j.reactfunctpolym.2012.08.004 SN - 1381-5148 VL - 72 IS - 11 SP - 878 EP - 888 PB - Elsevier CY - Amsterdam ER - TY - JOUR A1 - Ast, Sandra A1 - Müller, Holger A1 - Flehr, Roman A1 - Klamroth, Tillmann A1 - Walz, Bernd A1 - Holdt, Hans-Jürgen T1 - High Na+ and K+-induced fluorescence enhancement of a pi-conjugated phenylaza-18-crown-6-triazol-substituted coumarin fluoroionophore JF - Chemical communications N2 - The new pi-conjugated 1,2,3-triazol-1,4-diyl fluoroionophore 1 generated via Cu(I) catalyzed [3 + 2] cycloaddition shows high fluorescence enhancement factors (FEF) in the presence of Na+ (FEF = 58) and K+ (FEF = 27) in MeCN and high selectivity towards K+ under simulated physiological conditions (160 mM K+ or Na+, respectively) with a FEF of 2.5 for K+. Y1 - 2011 U6 - https://doi.org/10.1039/c0cc04370b SN - 1359-7345 VL - 47 IS - 16 SP - 4685 EP - 4687 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Schwarze, Thomas A1 - Kelling, Alexandra A1 - Müller, Holger A1 - Trautmann, Michael A1 - Klamroth, Tillmann A1 - Baumann, Otto A1 - Strauch, Peter A1 - Holdt, Hans-Jürgen T1 - N-2-Pyridinylmethyl-N '-arylmethyl-diaminomaleonitriles: New Highly Selective Chromogenic Chemodosimeters for Copper(II) JF - Chemistry - a European journal KW - amides KW - chemodosimeter KW - colorimetric detection KW - copper KW - sensors KW - UV KW - Vis spectroscopy Y1 - 2012 U6 - https://doi.org/10.1002/chem.201201731 SN - 0947-6539 VL - 18 IS - 34 SP - 10506 EP - 10510 PB - Wiley-VCH CY - Weinheim ER - TY - GEN A1 - Kirste, Matthias A1 - Brietzke, Thomas Martin A1 - Holdt, Hans-Jürgen A1 - Schilde, Uwe T1 - The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂ T2 - Postprints der Universität Potsdam Mathematisch-Naturwissenschaftliche Reihe N2 - C₁₈H₁₀N₂, monoclinic, P2₁/c (no. 14), a=7.9297(9) Å, b=11.4021(14) Å, c=13.3572(15) Å, β=105.363(8)°, V =1164.5(2) ų, Z =4, Rgt(F)=0.0325, wRref(F²)=0.0774, T =210(2) K. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 752 Y1 - 2019 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-436501 SN - 1866-8372 IS - 752 ER - TY - GEN A1 - Grunwald, Nicolas A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen A1 - Schilde, Uwe T1 - The crystal structure of 1,1′-bisisoquinoline, C18H12N2 N2 - C18H12N2, tetragonal, I41/a (no. 88), a=13.8885(6) Å, c=13.6718(6) Å, V =2637.2(3) Å3, Z =8, Rgt(F)=0.0295, wRref(F2)=0.0854, T =210 K. CCDC no.: 631823 T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 380 Y1 - 2017 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-401952 ER - TY - JOUR A1 - Hahn, Simone A1 - Träger, Juliane A1 - Holdt, Hans-Jürgen T1 - Solid-Phase extraction of Pt(IV) with Dialkyl-(hexane-1,6-diyl) phosphate modified merrifield resins from aqueous chloride media in column operations JF - Separation and purification technology N2 - A series of three dialkyl phosphate resins with a Merrifield resin support was used to extract platinum from acidic media. In column operations total capacities of 85-130 mg/g were gained. The presence of palladium and rhodium results in the order: Pt(IV) > Pd(II) >> Rh(III). From a leach liquor gained from spent automotive catalysts metals forming anionic chloro complexes are co-extracted only to a small extent. However, in order to separate and enrich platinum a selective back-extraction can be done with a sodium thiocyanate solution. A second elution step with acidic thiourea leads to a mixed solution of palladium and rhodium. KW - platinum KW - column operation mode KW - phosphate KW - solid-phase extraction Y1 - 2015 U6 - https://doi.org/10.1080/01496395.2014.968264 SN - 0149-6395 SN - 1520-5754 VL - 50 IS - 2 SP - 191 EP - 206 PB - Taylor & Francis Group CY - Philadelphia ER - TY - JOUR A1 - Kirste, Matthias A1 - Brietzke, Thomas Martin A1 - Holdt, Hans-Jürgen A1 - Schilde, Uwe T1 - The crystal structure of 1,12-diazaperylene, C₁₈H₁₀N₂ JF - Zeitschrift für Kristallographie - New Crystal Structures N2 - C₁₈H₁₀N₂, monoclinic, P2₁/c (no. 14), a=7.9297(9) Å, b=11.4021(14) Å, c=13.3572(15) Å, β=105.363(8)°, V =1164.5(2) ų, Z =4, Rgt(F)=0.0325, wRref(F²)=0.0774, T =210(2) K. Y1 - 2019 U6 - https://doi.org/10.1515/NCRS-2019-0385 SN - 2196-7105 SN - 2194-4946 VL - 234 IS - 6 SP - 1255 EP - 1257 PB - De Gruyter CY - Berlin ER - TY - JOUR A1 - Grunwald, Nicolas A1 - Kelling, Alexandra A1 - Holdt, Hans-Jürgen A1 - Schilde, Uwe T1 - The crystal structure of 1,1′-bisisoquinoline, C18H12N2 JF - Zeitschrift für Kristallographie : international journal for structural, physical and chemical aspects of crystalline materials. New crystal structures N2 - C18H12N2, tetragonal, I41/a (no. 88), a=13.8885(6) Å, c=13.6718(6) Å, V =2637.2(3) Å3, Z =8, Rgt(F)=0.0295, wRref(F2)=0.0854, T =210 K. CCDC no.: 631823 Y1 - 2017 U6 - https://doi.org/10.1515/ncrs-2017-0088 VL - 232 IS - 5 SP - 839 EP - 841 PB - de Gruyter CY - Berlin ER - TY - JOUR A1 - Starke, Ines A1 - Koch, Andreas A1 - Kammer, Stefan A1 - Holdt, Hans-Jürgen A1 - Möller, Heiko Michael T1 - Electrospray mass spectrometry and molecular modeling study of formation and stability of silver complexes with diazaperylene and bisisoquinoline JF - Journal of mass spectrometry N2 - The complex formation of the following diazaperylene ligands (L) 1,12-diazaperylene 1, 1,1-bisisoquinoline 2, 2,11-disubstituted 1,12-diazaperylenes (alkyl=methyl, ethyl, isopropyl, 3, 5, 7), 3,3-disubstituted 1,1-bisisoquinoline (alkyl=methyl, ethyl, isopropyl, 4, 6, 8 and with R=phenyl, 11 and with pyridine 12), and the 5,8-dimethoxy-substituted diazaperylene 9, 6,6-dimethoxy-substituted bisisoquinoline 10 with AgBF4 was investigated. Collision-induced dissociation measurements were used to evaluate the relative stabilities of the ligands themselves and for the [1:1](+) complexes as well as for the homoleptic and heteroleptic silver [1:2](+) complexes in the gas phase. This method is very useful in rapid screening of the stabilities of new complexes in the gas phase. The influence of the spatial arrangement of the ligands and the type of substituents employed for the complexation were examined. The effect of the preorganization of the diazaperylene on the threshold activation voltages and thus of the relative binding energies of the different complexes are discussed. Density functional theory calculations were used to calculate the optimized structures of the silver complexes and compared with the stabilities of the complexes in the gas phase for the first time. KW - electrospray ionization mass spectrometry and modeling KW - silver(1) complexes KW - stability Y1 - 2018 U6 - https://doi.org/10.1002/jms.4071 SN - 1076-5174 SN - 1096-9888 VL - 53 IS - 5 SP - 408 EP - 418 PB - Wiley CY - Hoboken ER - TY - JOUR A1 - Schwarze, Thomas A1 - Riemer, Janine A1 - Holdt, Hans-Jürgen T1 - A Ratiometric Fluorescent Probe for K+ in Water Based on a Phenylaza-18-Crown-6 Lariat Ether JF - Chemistry - a European journal N2 - This work presents two molecular fluorescent probes 1 and 2 for the selective determination of physiologically relevant K+ levels in water based on a highly K+/Na+ selective building block, the o-(2-methoxyethoxy)phenylaza-18-crown-6 lariat ether unit. Fluorescent probe 1 showed a high K+-induced fluorescence enhancement (FE) by a factor of 7.7 of the anthracenic emission and a dissociation constant (K-d) value of 38mm in water. Further, for 2+K+, we observed a dual emission behavior at 405 and 505nm. K+ increases the fluorescence intensity of 2 at 405nm by a factor of approximately 4.6 and K+ decreases the fluorescence intensity at 505nm by a factor of about 4.8. Fluorescent probe 2+K+ exhibited a K-d value of approximately 8mm in Na+-free solutions and in combined K+/Na+ solution a similar K-d value of about 9mm was found, reflecting the high K+/Na+ selectivity of 2 in water. Therefore, 2 is a promising fluorescent tool to measure ratiometrically and selectively physiologically relevant K+ levels. KW - charge transfer KW - crown compounds KW - fluorescence KW - potassium KW - ratiometric sensors Y1 - 2018 U6 - https://doi.org/10.1002/chem.201802306 SN - 0947-6539 SN - 1521-3765 VL - 24 IS - 40 SP - 10116 EP - 10121 PB - Wiley-VCH CY - Weinheim ER - TY - JOUR A1 - Mickler, Wulfhard A1 - Bukowsky, Heinz A1 - Holdt, Hans-Jürgen T1 - Separation of Palladium(II) with immobilized Maleonitrile-Dithiocrown ethers N2 - Especially sulphur containing compounds are suitable for the separation of noble metals. 1,2-Dithioethenes are weak chelate-forming ligands and in the case of bis(methylthio)maleo-nitrile the donor power of both of the sulphur atoms is further decreased by the electron withdrawing effect of the cyanogroups. Crowned dithiomaleonitrile are macrocyclic chelate ligands which extract Pd(II) at sufficient rate in a very good yields. The synthesis of the immobilised ligands proceeds from the 2-allyloxy-1,2-propanediol forming the dicar-bon acid which is reduced to the diole. With the help of thionylchloride the dichloro compound is synthe-sized forming the macrocycle together with a dithiolate (1,2-disodium-1,2-dicyanethene-1,2-dithiolate, 1,2-disodium-4-methylbenzene-1,2-dithiolate) at high dilution conditions. The allylsubstituted crown ether is sillylated and the resulting alkoxysilane is immobilised onto activated silica gel. The extraction results with crown ethers are compared with that achieved with the help of substituted ß- diketones and 4-acyl-5-pyrazolones. By modification of the cavity of the macrocyclus the extraction rate increases from the acyclic compound through maleonitrile-dithio-21-crown-7, maleonitrile-dithio-15-crown-5 and maleonitrile-18-crown-6. The best results can be observed at the maleonitrile-dithio-12-crown-4. The rise of the function log D= f(log L) gives the composition of the extracted compounds as 1:1. The separa-tion is unsatisfactory in the case of Ag(I), Hg(II), Pt(II), Tl (I) and the most 3d-elements. Summarizing, a very good separation of palladium from the examined elements can be specified. Additional to the extraction experiments, as well as the crystal structures and by UV spectroscopy the for- mation constants of selected chelates were determined. Y1 - 2002 ER -