TY - JOUR A1 - Wagner, Sabine A1 - Zapata, Carlos A1 - Wan, Wei A1 - Gawlitza, Kornelia A1 - Weber, M. A1 - Rurack, Knut T1 - Role of Counterions in Molecularly Imprinted Polymers for Anionic Species N2 - Small-molecule oxoanions are often imprinted noncovalently as carboxylates into molecularly imprinted polymers (MIPs), requiring the use of an organic counterion. Popular species are either pentamethylpiperidine (PMP) as a protonatable cation or tetraalkylammonium (TXA) ions as permanent cations. The present work explores the influence of the TXA as a function of their alkyl chain length, from methyl to octyl, using UV/vis absorption, fluorescence titrations, and HPLC as well as MD simulations. Protected phenylalanines (Z-L/D-Phe) served as templates/analytes. While the influence of the counterion on the complex stability constants and anion-induced spectral changes shows a monotonous trend with increasing alkyl chain length at the prepolymerization stage, the cross-imprinting/rebinding studies showed a unique pattern that suggested the presence of adaptive cavities in the MIP matrix, related to the concept of induced fit of enzyme−substrate interaction. Larger cavities formed in the presence of larger counterions can take up pairs of Z-X-Phe and smaller TXA, eventually escaping spectroscopic detection. Correlation of the experimental data with the MD simulations revealed that counterion mobility, the relative distances between the three partners, and the hydrogen bond lifetimes are more decisive for the response features observed than actual distances between interacting atoms in a complex or the orientation of binding moieties. TBA has been found to yield the highest imprinting factor, also showing a unique dual behavior regarding the interaction with template and fluorescent monomer. Finally, interesting differences between both enantiomers have been observed in both theory and experiment, suggesting true control of enantioselectivity. The contribution concludes with suggestions for translating the findings into actual MIP development. KW - Anion receptors KW - Fluorescence sensing KW - Molecular dynamics simulations KW - Molecularly imprinted polymers KW - Rational design PY - 2018 U6 - https://doi.org/10.1021/acs.langmuir.8b00500 SN - 0743-7463 VL - 34 IS - 23 SP - 6963 EP - 6975 PB - American Chemical Society CY - Washington, D.C. AN - OPUS4-45399 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Costa, Elena A1 - Climent Terol, Estela A1 - Gawlitza, Kornelia A1 - Wan, Wei A1 - Weller, Michael G. A1 - Rurack, Knut T1 - Optimization of analytical assay performance of antibody-gated indicator-releasing mesoporous silica particles N2 - Antibody-gated indicator delivery (gAID) systems based on mesoporous silica nano- and microparticle scaffolds are a promising class of materials for the sensitive chemical detection of small-molecule analytes in simple test formats such as lateral flow assays (LFAs) or microfluidic chips. Their architecture is reminiscent of drug delivery systems, only that reporter molecules instead of drugs are stored in the voids of a porous host particle. In addition, the pores are closed with macromolecular “caps” through a tailored “gatekeeping” recognition chemistry so that the caps are opened when an analyte has reacted with a “gatekeeper”. The subsequent uncapping leads to a release of a large number of indicator molecules, endowing the system with signal amplification features. Particular benefits of such systems are their modularity and adaptability. With the example of the immunochemical detection of type-I pyrethroids by fluorescent dye-releasing gAID systems, the influence of several tuning modes on the optimisation of such hybrid sensory materials is introduced here. In particular, different mesoporous silica supports (from nano- and microparticles to platelets and short fibres), different functionalisation routes and different loading sequences were assessed. The materials’ performances were evaluated by studying their temporal response behaviour and detection sensitivity, including the tightness of pore closure (through the amount of blank release in the absence of analyte) and the release kinetics. Our results indicate that the better the paratope-accommodating Fab region of the antibody “cap” fits into the host material's pore opening, the better the closing/opening mechanism can be controlled. Because such materials are well-suited for LFAs, performance assessment included a test-strip format besides conventional assays in suspension. In combination with dyes as indicators and smartphones for read-out, simple analytical tests for use by untrained personnel directly at a point-of-need such as an aeroplane cabin can be devised, allowing for sensitivities down to the μg kg−1 range in <5 min with case-required selectivities. KW - Antibody-gated indicator delivery KW - Lateral flow assay KW - SBA-15 KW - SBA-16 KW - Type-I pyrethroids KW - Phenothrin KW - Permethrin KW - Etofenprox KW - Amplification KW - Biosensors KW - Immunoassays KW - Mesoporous particles KW - Optical detection PY - 2020 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:b43-517053 VL - 8 IS - 22 SP - 4950 EP - 4961 PB - Royal Society of Chemistry AN - OPUS4-51705 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - CHAP A1 - Gawlitza, Kornelia A1 - Wan, Wei A1 - Wagner, Sabine A1 - Rurack, Knut ED - Tiwari, Ashutosh ED - Uzun, Lokman T1 - Fluorescent Molecularly Imprinted Polymers N2 - An ideal sensor system is a combination of a selective receptor, an effective transducer, and a sensitive detector. To utilize molecularly imprinted polymers (MIPs) as responsive recognition phases in sensors, the employment of fluorescent molecules or nanoparticles (NPs) that show prominent changes in their spectroscopic properties after binding of the target molecule in the MIP’s cavity is particularly attractive. Such fluorescent MIPs (fMIPs) act through target-induced quenching, enhancement, or spectral shifts of the fluorescence. This contribution introduces different strategies of incorporation of fluorescent dyes, probes, and NPs into fMIPs. In addition, various sensing mechanisms are reviewed, and depending on the application of the sensor, the different deployable formats, their advantages, drawbacks, and impact will be presented and discussed. KW - Dyes KW - Fluorescence KW - Molecular imprinted polymers KW - Quantum dots KW - Sensors PY - 2017 SN - 978-1-119-33629-7 SP - 89 EP - 128 PB - Scrivener Publishing, WILEY CY - Beverly, MA ET - 1 AN - OPUS4-38798 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -