92a55b23c220487d7f351a09a501db89 pmc_11722672.pdf 48ac5b8bde126adb81212df94be918fdcb9d328c pmc_11722672.pdf 145e8c87b37644f1c00fc770f8debf1320cfd9ecd79bfe8e5e3e227b5b543d4c pmc_11722672.pdf Title: Peroxidase (POD) Mimicking Activity of Different Types of Poly(ethyleneimine)-Mediated Prussian Blue Nanoparticles Subject: Prussian blue nanoparticles (PBNPs) have been identified as a promising candidate for biomimetic peroxidase (POD)-like activity, specifically due to the metal centres (Fe3+/Fe2+) of Prussian blue (PB), which have the potential to function as catalytically active centres. The decoration of PBNPs with desired functional polymers (such as amino- or carboxylate-based) primarily facilitates the subsequent linkage of biomolecules to the nanoparticles for their use in biosensor applications. Thus, the elucidation of the catalytic POD mimicry of these systems is of significant scientific interest but has not been investigated in depth yet. In this report, we studied a series of poly(ethyleneimine) (PEI)-mediated PBNPs (PB/PEI NPs) prepared using various synthesis protocols. The resulting range of particles with varying size (~19–92 nm) and shape combinations were characterised in order to gain insights into their physicochemical properties. The POD-like nanozyme activity of these nanoparticles was then investigated by utilising a 3,3',5,5'-tetramethylbenzidine (TMB)/H2O2 system, with the catalytic performance of the natural enzyme horseradish peroxidase (HRP) serving as a point of comparison. It was shown that most PB/PEI NPs displayed higher catalytic activity than the PBNPs, with higher activity observed in particles of smaller size, higher Fe content, and higher Fe2+/Fe3+ ratio. Furthermore, the nanoparticles demonstrated enhanced chemical stability in the presence of acid, sodium azide, or high concentrations of H2O2 when compared to HRP, confirming the viability of PB/PEI NPs as a promising nanozymatic material. This study disseminates fundamental knowledge on PB/PEI NPs and their POD-like activities, which will facilitate the selection of an appropriate particle type for future biosensor applications. Keywords: Prussian blue nanoparticles (PBNPs); nanozyme; poly(ethyleneimine) (PEI); peroxidase mimetic; amino-rich polymers; catalysts; catalytic inhibition; cyano-bridged coordination polymers Author: Udara Bimendra Gunatilake, Briza Pérez-López, Maria Urpi, Judit Prat-Trunas, Gerard Carrera-Cardona, Gautier Félix, Saad Sene, Mickaël Beaudhuin, Jean-Charles Dupin, Joachim Allouche, Yannick Guari, Joulia Larionova and Eva Baldrich Creator: LaTeX with hyperref Producer: pdfTeX-1.40.25 CreationDate: Fri Jan 10 11:41:50 2025 CET ModDate: Fri Jan 10 11:51:28 2025 CET Custom Metadata: no Metadata Stream: no Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 21 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 5252041 bytes Optimized: no PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- HJOMHV+VnURWPalladioL-Bold Type 1 Custom yes yes yes 10 0 EPEYZQ+URWPalladioL-Roma Type 1 Custom yes yes yes 16 0 AGSPQJ+URWPalladioL-Bold Type 1 Custom yes yes yes 22 0 HISNGS+URWPalladioL-Ital Type 1 Custom yes yes yes 27 0 LYYSLR+CMSY10 Type 1 Builtin yes yes yes 32 0 EXVEHZ+VnURWPalladioL Type 1 Custom yes yes yes 37 0 KGTBTS+URWPalladioL-BoldItal Type 1 Custom yes yes yes 66 0 IZJBLV+EURM10 Type 1 Builtin yes yes yes 77 0 CQEKYI+CMR10 Type 1 Builtin yes yes yes 82 0 CIDFont+F3 CID TrueType Identity-H yes no yes 95 0 CIDFont+F1 CID TrueType Identity-H yes no yes 103 0 CIDFont+F2 CID TrueType Identity-H yes no yes 111 0 CIDFont+F3 CID TrueType Identity-H yes no yes 128 0 CIDFont+F1 CID TrueType Identity-H yes no yes 136 0 CIDFont+F2 CID TrueType Identity-H yes no yes 144 0 CIDFont+F3 CID TrueType Identity-H yes no yes 158 0 CIDFont+F1 CID TrueType Identity-H yes no yes 166 0 CIDFont+F2 CID TrueType Identity-H yes no yes 174 0 CIDFont+F3 CID TrueType Identity-H yes no yes 188 0 CIDFont+F1 CID TrueType Identity-H yes no yes 196 0 CIDFont+F2 CID TrueType Identity-H yes no yes 204 0 MPUDFL+PazoMath Type 1 Builtin yes yes yes 217 0 CIDFont+F3 CID TrueType Identity-H yes no yes 224 0 CIDFont+F1 CID TrueType Identity-H yes no yes 232 0 CIDFont+F2 CID TrueType Identity-H yes no yes 240 0 CIDFont+F6 CID TrueType Identity-H yes no yes 248 0 CIDFont+F3 CID TrueType Identity-H yes no yes 262 0 CIDFont+F1 CID TrueType Identity-H yes no yes 270 0 CIDFont+F2 CID TrueType Identity-H yes no yes 278 0 CIDFont+F3 CID TrueType Identity-H yes no yes 292 0 CIDFont+F1 CID TrueType Identity-H yes no yes 300 0 CIDFont+F2 CID TrueType Identity-H yes no yes 308 0 CIDFont+F3 CID TrueType Identity-H yes no yes 322 0 CIDFont+F1 CID TrueType Identity-H yes no yes 330 0 CIDFont+F2 CID TrueType Identity-H yes no yes 338 0 AOGJAB+PalatinoLinotype,Bold TrueType WinAnsi yes yes no 360 0 AOGJAC+PalatinoLinotype CID TrueType Identity-H yes yes yes 363 0 AOGJAD+PalatinoLinotype TrueType WinAnsi yes yes no 369 0 AOGJAF+PalatinoLinotype,Italic TrueType WinAnsi yes yes no 372 0 AOGJGE+PalatinoLinotype TrueType MacRoman yes yes no 375 0 Jhove (Rel. 1.28.0, 2023-05-18) Date: 2025-02-06 02:44:05 CET RepresentationInformation: pmc_11722672.pdf ReportingModule: PDF-hul, Rel. 1.12.4 (2023-03-16) LastModified: 2025-01-17 02:39:57 CET Size: 5252041 Format: PDF Version: 1.7 Status: Well-Formed and valid SignatureMatches: PDF-hul MIMEtype: application/pdf PDFMetadata: Objects: 603 FreeObjects: 1 IncrementalUpdates: 0 DocumentCatalog: PageLayout: SinglePage PageMode: UseNone Outlines: Item: Title: Introduction Destination: section.1 Item: Title: Experimental Destination: section.2 Children: Item: Title: In Situ Synthesis of PB/PEI Nanoparticles by Controlled Coprecipitation (C1) Destination: subsection.2.1 Item: Title: Synthesis of PB/PEI Nanoparticles by Thermally Reductive Process Destination: subsection.2.2 Children: Item: Title: T1 PB/PEI Nanoparticles Destination: subsubsection.2.2.1 Item: Title: T2 PB/PEI Nanoparticles Destination: subsubsection.2.2.2 Item: Title: T3 PB/PEI Nanoparticles Destination: subsubsection.2.2.3 Item: Title: Synthesis of PB/PEI Nanoparticles by Custom Home-Made Vortex Process (V1) Destination: subsection.2.3 Item: Title: Investigation of POD-like Catalytic Activity of the Nanoparticles Destination: subsection.2.4 Item: Title: PB and PB/PEI Nanoparticle Characterisation Destination: subsection.2.5 Item: Title: Results and Discussion Destination: section.3 Item: Title: Conclusions Destination: section.4 Item: Title: References Destination: appendix.A. Info: Title: Peroxidase (POD) Mimicking Activity of Different Types of Poly(ethyleneimine)-Mediated Prussian Blue Nanoparticles Author: Udara Bimendra Gunatilake, Briza Pérez-López, Maria Urpi, Judit Prat-Trunas, Gerard Carrera-Cardona, Gautier Félix, Saad Sene, Mickaël Beaudhuin, Jean-Charles Dupin, Joachim Allouche, Yannick Guari, Joulia Larionova and Eva Baldrich Subject: Prussian blue nanoparticles (PBNPs) have been identified as a promising candidate for biomimetic peroxidase (POD)-like activity, specifically due to the metal centres (Fe3+/Fe2+) of Prussian blue (PB), which have the potential to function as catalytically active centres. The decoration of PBNPs with desired functional polymers (such as amino- or carboxylate-based) primarily facilitates the subsequent linkage of biomolecules to the nanoparticles for their use in biosensor applications. Thus, the elucidation of the catalytic POD mimicry of these systems is of significant scientific interest but has not been investigated in depth yet. In this report, we studied a series of poly(ethyleneimine) (PEI)-mediated PBNPs (PB/PEI NPs) prepared using various synthesis protocols. The resulting range of particles with varying size (~19 92 nm) and shape combinations were characterised in order to gain insights into their physicochemical properties. The POD-like nanozyme activity of these nanoparticles was then investigated by utilising a 3,3',5,5'-tetramethylbenzidine (TMB)/H2O2 system, with the catalytic performance of the natural enzyme horseradish peroxidase (HRP) serving as a point of comparison. It was shown that most PB/PEI NPs displayed higher catalytic activity than the PBNPs, with higher activity observed in particles of smaller size, higher Fe content, and higher Fe2+/Fe3+ ratio. Furthermore, the nanoparticles demonstrated enhanced chemical stability in the presence of acid, sodium azide, or high concentrations of H2O2 when compared to HRP, confirming the viability of PB/PEI NPs as a promising nanozymatic material. This study disseminates fundamental knowledge on PB/PEI NPs and their POD-like activities, which will facilitate the selection of an appropriate particle type for future biosensor applications. 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