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The thiophene-modified iron porphyrin FeT3ThP and the respective iron Hangman porphyrin FeH3ThP, incorporating a carboxylic acid hanging group in the second coordination sphere of the iron center, were electropolymerized on glassy carbon electrodes using 3,4-ethylenedioxythiophene (EDOT) as co-monomer. Scanning electron microscopy images and Resonance Raman spectra demonstrated incorporation of the porphyrin monomers into a fibrous polymer network. Porphyrin/polyEDOT films catalyzed the reduction of molecular oxygen in a four-electron reaction to water with onset potentials as high as +0.14V vs. Ag/AgCl in an aqueous solution of pH7. Further, FeT3ThP/polyEDOT films showed electrocatalytic activity towards reduction of hydrogen peroxide at highly positive potentials, which was significantly enhanced by introduction of the carboxylic acid hanging group in FeH3ThP. The second coordination sphere residue promotes formation of a highly oxidizing reaction intermediate, presumably via advantageous proton supply, as observed for peroxidases and catalases making FeH3ThP/polyEDOT films efficient mimics of heme enzymes.
Electrochemical biosensors employing natural and artificial heme peroxidases on semiconductors
(2020)
Heme peroxidases are widely used as biological recognition elements in electrochemical biosensors for hydrogen peroxide and phenolic compounds. Various nature-derived and fully synthetic heme peroxidase mimics have been designed and their potential for replacing the natural enzymes in biosensors has been investigated. The use of semiconducting materials as transducers can thereby offer new opportunities with respect to catalyst immobilization, reaction stimulation, or read-out. This review focuses on approaches for the construction of electrochemical biosensors employing natural heme peroxidases as well as various mimics immobilized on semiconducting electrode surfaces. It will outline important advances made so far as well as the novel applications resulting thereof.
Molecularly imprinted polymers (MIPs) have the potential to complement antibodies in bioanalysis, are more stable under harsh conditions, and are potentially cheaper to produce. However, the affinity and especially the selectivity of MIPs are in general lower than those of their biological pendants. Enzymes are useful tools for the preparation of MIPs for both low and high-molecular weight targets: As a green alternative to the well-established methods of chemical polymerization, enzyme-initiated polymerization has been introduced and the removal of protein templates by proteases has been successfully applied. Furthermore, MIPs have been coupled with enzymes in order to enhance the analytical performance of biomimetic sensors: Enzymes have been used in MIP-sensors as tracers for the generation and amplification of the measuring signal. In addition, enzymatic pretreatment of an analyte can extend the analyte spectrum and eliminate interferences.
Molecularly imprinted polymers (MIPs) have the potential to complement antibodies in bioanalysis, are more stable under harsh conditions, and are potentially cheaper to produce. However, the affinity and especially the selectivity of MIPs are in general lower than those of their biological pendants. Enzymes are useful tools for the preparation of MIPs for both low and high-molecular weight targets: As a green alternative to the well-established methods of chemical polymerization, enzyme-initiated polymerization has been introduced and the removal of protein templates by proteases has been successfully applied. Furthermore, MIPs have been coupled with enzymes in order to enhance the analytical performance of biomimetic sensors: Enzymes have been used in MIP-sensors as tracers for the generation and amplification of the measuring signal. In addition, enzymatic pretreatment of an analyte can extend the analyte spectrum and eliminate interferences.
The heme-undecapeptide microperoxidase-11 (MP-11) was immobilized on mesoporous antimony-doped tin oxide (ATO) thin-film electrodes modified with the positively charged binding promotor polydiallyldimethylammonium chloride. Surface concentrations of MP-11 of 1.5 nmol cm(-2) were sufficiently high to enable spectroelectrochemical analyses. UV/Vis spectroscopy and resonance Raman spectroscopy revealed that immobilized MP-11 adopts a six-coordinated low-spin conformation, as in solution in the presence of a polycation. Cathodic reduction of hydrogen peroxide at potentials close to +500mV versus Ag/AgCl indicates that the reaction proceeds via a Compound I-type like intermediate, analogous to natural peroxidases, and confirms mesoporous ATO as a suitable host material for adsorbing the heme-peptide in its native state. A hydrogen peroxide sensor is proposed by using the bioelectrocatalytic properties of the MP-11-modified ATO.
The present study reports a facile approach for sulfite biosensing, based on enhanced direct electron transfer of a human sulfite oxidase (hSO) immobilized on a gold nanoparticles modified electrode. The spherical core shell AuNPs were prepared via a new method by reduction of HAuCl4 with branched poly(ethyleneimine) in an ionic liquids resulting particles with a diameter less than 10 nm. These nanoparticles were covalently attached to a mercaptoundecanoic acid modified Au-electrode where then hSO was adsorbed and an enhanced interfacial electron transfer and electrocatalysis was achieved. UV/Vis and resonance Raman spectroscopy, in combination with direct protein voltammetry, are employed for the characterization of the system and reveal no perturbation of the structural integrity of the redox protein. The proposed biosensor exhibited a quick steady-state current response, within 2 s, a linear detection range between 0.5 and 5.4 mu M with a high sensitivity (1.85 nA mu M-1). The investigated system provides remarkable advantages in the possibility to work at low applied potential and at very high ionic strength. Therefore these properties could make the proposed system useful in the development of bioelectronic devices and its application in real samples.
Binding of heme to the amyloid peptides A beta 40/42 is thought to be an initial step in the development of symptoms in the early stages of Alzheimer's disease by enhancing the intrinsic peroxidatic activity of heme. We found considerably higher acceleration of the reaction for the physiologically relevant neurotransmitters dopamine and serotonin than reported earlier for the artificial substrate 3,3',5,5'-tetramethylbenzidine (TMB). Thus, the binding of hemin to A beta peptides might play an even more crucial role in the early stages of Alzheimer's disease than deduced from these earlier results. To mimic complex formation, a new surface architecture has been developed: The interaction between the truncated amyloid peptide A beta 1-16 and hemin immobilized on an aminohexanethiol spacer on a gold electrode has been analyzed by cyclic voltammetry. The resulting complex has a redox pair with a 25 mV more cathodic formal potential than hemin alone.
The aromatic peroxygenase (APO; EC 1.11.2.1) from the agraric basidomycete Marasmius rotula (MroAPO) immobilized at the chitosan-capped gold-nanoparticle-modified glassy carbon electrode displayed a pair of redox peaks with a midpoint potential of -278.5 mV vs. AgCl/AgCl (1 M KCl) for the Fe(2+)/Fe(3+) redox couple of the heme-thiolate-containing protein. MroAPO oxidizes aromatic substrates such as aniline, p-aminophenol, hydroquinone, resorcinol, catechol, and paracetamol by means of hydrogen peroxide. The substrate spectrum overlaps with those of cytochrome P450s and plant peroxidases which are relevant in environmental analysis and drug monitoring. In M. rotula peroxygenase-based enzyme electrodes, the signal is generated by the reduction of electrode-active reaction products (e.g., p-benzoquinone and p-quinoneimine) with electro-enzymatic recycling of the analyte. In these enzyme electrodes, the signal reflects the conversion of all substrates thus representing an overall parameter in complex media. The performance of these sensors and their further development are discussed.
Background
Dietary calcium (Ca) concentrations might affect regulatory pathways within the Ca and vitamin D metabolism and consequently excretory mechanisms. Considering large variations in Ca concentrations of feline diets, the physiological impact on Ca homeostasis has not been evaluated to date. In the present study, diets with increasing concentrations of dicalcium phosphate were offered to ten healthy adult cats (Ca/phosphorus (P): 6.23/6.02, 7.77/7.56, 15.0/12.7, 19.0/17.3, 22.2/19.9, 24.3/21.6 g/kg dry matter). Each feeding period was divided into a 10-day adaptation and an 8-day sampling period in order to collect urine and faeces. On the last day of each feeding period, blood samples were taken.
Results
Urinary Ca concentrations remained unaffected, but faecal Ca concentrations increased (P < 0.001) with increasing dietary Ca levels. No effect on whole and intact parathyroid hormone levels, fibroblast growth factor 23 and calcitriol concentrations in the blood of the cats were observed. However, the calcitriol precursors 25(OH)D-2 and 25(OH)D-3, which are considered the most useful indicators for the vitamin D status, decreased with higher dietary Ca levels (P = 0.013 and P = 0.033). Increasing dietary levels of dicalcium phosphate revealed an acidifying effect on urinary fasting pH (6.02) and postprandial pH (6.01) (P < 0.001), possibly mediated by an increase of urinary phosphorus (P) concentrations (P < 0.001).
Conclusions
In conclusion, calcitriol precursors were linearly affected by increasing dietary Ca concentrations. The increase in faecal Ca excretion indicates that Ca homeostasis of cats is mainly regulated in the intestine and not by the kidneys. Long-term studies should investigate the physiological relevance of the acidifying effect observed when feeding diets high in Ca and P.
Background Dietary calcium (Ca) concentrations might affect regulatory pathways within the Ca and vitamin D metabolism and consequently excretory mechanisms. Considering large variations in Ca concentrations of feline diets, the physiological impact on Ca homeostasis has not been evaluated to date. In the present study, diets with increasing concentrations of dicalcium phosphate were offered to ten healthy adult cats (Ca/phosphorus (P): 6.23/6.02, 7.77/7.56, 15.0/12.7, 19.0/17.3, 22.2/19.9, 24.3/21.6 g/kg dry matter). Each feeding period was divided into a 10-day adaptation and an 8-day sampling period in order to collect urine and faeces. On the last day of each feeding period, blood samples were taken. Results Urinary Ca concentrations remained unaffected, but faecal Ca concentrations increased (P < 0.001) with increasing dietary Ca levels. No effect on whole and intact parathyroid hormone levels, fibroblast growth factor 23 and calcitriol concentrations in the blood of the cats were observed. However, the calcitriol precursors 25(OH)D-2 and 25(OH)D-3, which are considered the most useful indicators for the vitamin D status, decreased with higher dietary Ca levels (P = 0.013 and P = 0.033). Increasing dietary levels of dicalcium phosphate revealed an acidifying effect on urinary fasting pH (6.02) and postprandial pH (6.01) (P < 0.001), possibly mediated by an increase of urinary phosphorus (P) concentrations (P < 0.001). Conclusions In conclusion, calcitriol precursors were linearly affected by increasing dietary Ca concentrations. The increase in faecal Ca excretion indicates that Ca homeostasis of cats is mainly regulated in the intestine and not by the kidneys. Long-term studies should investigate the physiological relevance of the acidifying effect observed when feeding diets high in Ca and P.
Städte sind aufgrund ihrer Agglomeration von Bevölkerung, Sachwerten und Infrastrukturen in besonderem Maße von extremen Wetterereignissen wie Starkregen und Hitze betroffen. Zahlreiche Überflutungsereignisse infolge von Starkregen traten in den letzten Jahren in verschiedenen Regionen Deutschlands auf und führten nicht nur zu Schäden in zwei- bis dreistelliger Millionenhöhe, sondern auch zu Todesopfern. Und auch Hitzewellen, wie sie in den vergangenen Jahren vermehrt aufgetreten sind, bergen gesundheitliche Risiken, welche sich auch in verschiedenen Schätzungen zu Hitzetodesfällen wiederfinden.
Um diesen Risiken zu begegnen und Schäden infolge von Wetterextremen zu reduzieren, entwickeln viele Kommunen bereits Strategien und Konzepte im Kontext der Klimaanpassung und/oder setzen Anpassungsmaßnahmen um. Neben der Entwicklung und Umsetzung eigener Ideen orientieren sich Städte dabei u. a. an Leitfäden und Beispielen aus der Literatur, Erfahrungen aus anderen Städten oder an Ergebnissen aus Forschungsprojekten. Dieser Lern- und Transferprozess, der eine Übertragung von Maßnahmen oder Instrumenten der Klimaanpassung von einem Ort auf einen anderen beinhaltet, ist bislang noch unzureichend erforscht und verstanden.
Der vorliegende Bericht untersucht deshalb ebendiesen Lern- und Transferprozess zwischen sowie innerhalb von Städten sowie das Transferpotenzial konkreter Wissenstransfer-Medien, Instrumente und Maßnahmen. Damit wird das Ziel verfolgt, ein besseres Verständnis dieser Prozesse zu entwickeln und einen Beitrag zur Verbesserung des Transfers von kommunalen Klimaanpassungsaktivitäten zu leisten. Der vorliegende Inhalt baut dabei auf einer vorangegangenen Analyse des Forschungsstands zum Transfer von Policies durch Haupt et al. (2021) auf und versucht, den bereits generierten Wissensstand auf der Ebene von Policies nun um die Ebene konkreter Instrumente und Maßnahmen zu ergänzen sowie durch empirische Befunde zu ausgewählten Maßnahmen zu untermauern. Die Wissens- und Datengrundlage dieses Berichts umfasst einen Mix aus verschiedenen (Online)-Befragungen und Interviews mit Vertreter:innen relevanter Akteursgruppen, vor allem Vertreter:innen von Stadtverwaltungen, sowie den Erfahrungswerten der drei ExTrass-Fallstudienstädte Potsdam, Remscheid und Würzburg.
Nach einer Einleitung beschäftigt sich Kapitel 2 mit übergeordneten Faktoren der Übertragbarkeit bzw. des Transfers. Kapitel 2.1 bietet hierbei eine Zusammenfassung zum aktuellen Wissensstand hinsichtlich des Transfers von Policies im Bereich der städtischen Klimapolitik gemäß Haupt et al. (2021). Hier werden zentrale Kriterien für einen erfolgreichen Transfer herausgearbeitet, um einen Anknüpfungspunkt für die folgenden Inhalte und empirischen Befunde auf der Ebene konkreter Instrumente und Maßnahmen zu bieten. Kapitel 2.2 schließt hieran an und präsentiert Erkenntnisse aus einer weitreichenden Kommunalbefragung. Hierbei wurde untersucht ob und welche Klimaanpassungsmaßnahmen in den Städten bereits umgesetzt werden, welche fördernden und hemmenden Aspekte es dabei gibt und welche Erfahrungen beim Transfer von Wissen und Ideen bereits vorliegen.
Kapitel 3 untersucht die Rolle verschiedener Medien des Wissenstransfers und widmet sich dabei beispielhaft Leitfäden zur Klimaanpassung und Maßnahmensteckbriefen. Kapitel 3.1 beantwortet dabei Fragen nach der Relevanz und Zugänglichkeit von Leitfäden, deren Stärken und Schwächen, sowie konkreten Anforderungen vonseiten befragter Personen. Außerdem werden acht ausgewählte Leitfäden vorgestellt und komprimiert auf ihre Transferpotenziale hin eingeschätzt. Kapitel 3.2 betrachtet Maßnahmensteckbriefe als Medien des Wissenstransfers und arbeitet zentrale Aspekte für einen praxisrelevanten inhaltlichen Aufbau heraus, um basierend darauf einen Muster-Maßnahmensteckbrief für Klimaanpassungsmaßnahmen zu entwickeln und vorzuschlagen.
Kapitel 4 beschäftigt sich mit sehr konkreten kommunalen Erfahrungen rund um den Transfer von sieben ausgewählten Instrumenten und Maßnahmen und bietet zahlreiche empirische Befunde aus den Kommunen, basierend auf der Kommunalbefragung, verschiedenen Interviews und den Erfahrungen aus der Projektarbeit. Die folgenden sieben Instrumente und Maßnahmen wurden ausgewählt, um eine große Breite städtischer Klimaanpassungsaktivitäten zu betrachten: 1) Klimafunktionskarten (Stadtklimakarten), 2) Starkregengefahrenkarten, 3) Checklisten zur Klimaanpassung in der Bauleitplanung, 4) Verbot von Schottergärten in Bebauungsplänen, 5) Fassadenbegrünungen, 6) klimaangepasste Gestaltung von Grün- und Freiflächen sowie 7) Handlungsempfehlungen für Betreuungseinrichtungen zum Umgang mit Hitze und Starkregen. Für jede dieser Klimaanpassungsaktivitäten wird auf Ebene der Kommunen Ziel, Verbreitung und Erscheinungsformen, Umsetzung anhand konkreter Beispiele, fördernde und hemmende Faktoren sowievorliegende Erfahrungen zu und Hinweisen auf Transfer dargestellt.
Kapitel 5 schließt den vorliegenden Bericht ab, indem zentrale Transfer-Barrieren aus den gewonnenen Erkenntnissen aufgegriffen und entsprechende Empfehlungen an verschiedene Ebenen der Politik ausgesprochen werden. Diese Empfehlungen zur Verbesserung des Transfers von klimaanpassungsrelevanten Instrumenten, Strategien und Maßnahmen umfassen 1) die Verbesserung des Austauschs zwischen verschiedenen Städten, 2) die Verbesserung der Zugänglichkeit von Wissen und Erfahrungen, 3) die Schaffung von Vernetzungsstrukturen innerhalb von Städten sowie 4) bestehende Wissenslücken zu schließen.
Die Autor:innen des vorliegenden Berichts hoffen, durch die vielfältigen Untersuchungsaspekte einen Beitrag zum besseren Verständnis der Lern- und Transferprozesse und zur Verbesserung des Transfers kommunaler Klimaanpassungsaktivitäten zu leisten.