Lateral Flow Assay Biotesting by Utilizing Plasmonic Nanoparticles Made of Inexpensive Metals─Replacing Colloidal Gold.

Nanoparticles (NPs) can be conjugated with diverse biomolecules and employed in biosensing to detect target analytes in biological samples. This proven concept was primarily used during the COVID-19 pandemic with gold-NP-based lateral flow assays (LFAs). Considering the gold price and its worldwide depletion, here we show that novel plasmonic NPs based on inexpensive metals, titanium nitride (TiN) and copper covered with a gold shell (Cu@Au), perform comparable to or even better than gold nanoparticles. After conjugation, these novel nanoparticles provided high figures of merit for LFA testing, such as high signals and specificity and robust naked-eye signal recognition. Since the main cost of Au NPs in commercial testing kits is the colloidal synthesis, our development with the Cu@Au and the laser-ablation-fabricated TiN NPs is exciting, offering potentially inexpensive plasmonic nanomaterials for various bioapplications. Moreover, our machine learning study showed that biodetection with TiN is more accurate than that with Au.

Visible Light-Assisted Coordination of a Rh(III)-BODIPY Complex to Guanine.

Most photodynamic therapeutics (PDTs) used in cancer treatment require oxygen to work efficiently to terminate cancer cells. These PDTs do not efficiently treat tumors in hypoxic conditions. Rh(III) polypyridyl complexes have been reported to have a photodynamic therapeutic effect in hypoxic conditions when exposed to UV light. UV light can damage tissue and cannot penetrate deep to reach cancer cells. This work proposes the coordination of a BODIPY fluorophore to a rhodium metal center to form a Rh(III)-BODIPY complex that enhances the reactivity of the rhodium under visible light. This complex formation is facilitated with the BODIPY as the highest occupied molecular orbital (HOMO), while the lowest unoccupied molecular orbital (LUMO) is localized on the Rh(III) metal center. Irradiation of the BODIPY transition at ∼524 nm can cause an indirect electron transfer from the orbital of the BODIPY-centered HOMO to the Rh(III)-centered LUMO, populating the dσ* orbital. In addition, photo binding of the Rh complex covalently coordinated to the N (7) position of guanine in an aqueous solution was also observed by mass spectrometry after chloride dissociation upon irradiation with green visible light (532 nm LED). Calculated thermochemistry values of the Rh complex reaction in methanol, acetonitrile, water, and guanine were determined using DFT calculations. All enthalpic reactions and Gibbs free energies were identified as endothermic and nonspontaneous, respectively. This observation supports the chloride dissociation using 532 nm light. This Rh(III)-BODIPY complex expands the class of visible light-activated Rh(III) photocisplatin analogs that may have potential photodynamic therapeutic activity for the treatment of cancers in hypoxic conditions.

Insights on the Molecular Characteristics of Molecularly Imprinted Polymers as Monitored by Sum Frequency Generation Spectroscopy.

Sensing in molecularly imprinted polymers (MIPs) requires specific interactions of the imprinted polymer and the approaching template molecule. These interactions are affected by the morphology of the polymer surface, the affinity of the template molecule to the polymer network, and the steric approach. In this particular study, a template molecule, metronidazole, is studied with respect to the typically used methacrylic acid-based imprinted polymer using a combination of bulk and surface techniques. The resulting infrared (IR) spectra exhibited the presence of the template molecule in the polymer matrix as well as their efficient removal after washing. Dipping of the MIP according to what is expected of facile sensing in an aqueous solution of metronidazole did not show any presence of the template molecule in the bulk of the MIP, as observed by IR spectroscopy. However, using sum frequency generation (SFG) spectroscopy, the CH aromatic stretch of the imidazole ring positioned at ∼3100 cm-1 was observed at the polymer surface, including its inner pores or cavities, and at the buried polymer-fused silica interface after dipping. SFG studies have also shown the vibrational signatures of the polymer matrix, the presence of the template molecule on the surface, and the detection of residual template molecules after washing. Increasing the washing time to 50 min has proven to be less effective than increasing the washing cycles to three. However, after the third cycle, reorganization of the polymer matrix was evident as also the complete removal of the template molecule. The observed changes from the acquired images using scanning electron microscopy and atomic force microscopy show the structural morphologies of MIPs and a good distribution of the pores across the MIP surface. The study demonstrates the importance of combining both bulk and surface characterization in providing insight into the template molecule-polymer network interactions.

Successive Surface Reactions on Hydrophilic Silica for Modified Magnetic Nanoparticle Attachment Probed by Sum-Frequency Generation Spectroscopy.

Successive surface reactions on hydrophilic silica substrates were designed and performed to immobilize ethanolamine-modified magnetic ferrite-based nanoparticle (NP) for surface characterization. The various surfaces were monitored using sum-frequency generation (SFG) spectroscopy. The surface of the hydrophilic quartz substrate was first converted to a vinyl-terminated surface by utilizing a silanization reaction, and then, the surface functional groups were converted to carboxylic-terminated groups via a thiol-ene reaction. The appearance and disappearance of the vinyl (═CH2) peak at ∼2990 cm-1 in the SFG spectra were examined to confirm the success of the silanization and thiol-ene reactions, respectively. Acyl chloride (-COCl) formation from carboxy (-COOH) functional group was then performed for further attachment of magnetic amine-functionalized magnesium ferrite nanoparticles (NPs) via amide bond formation. The scattered NPs attached on the modified silica substrate was then used to study the changes in the spectral profile of the ethanolamine modifier of the NPs for in situ lead(II) (Pb2+) adsorption at the solid-liquid interface using SFG spectroscopy. However, due to the limited number of NPs attached and sensitivity of SFG spectroscopy toward expected change in the modifier spectroscopically, no significant change was observed in the SFG spectrum of the modified silica with magnetic NPs during exposure to Pb2+ solution. Nevertheless, SFG spectroscopy as a surface technique successfully monitored the modifications from a clean fused substrate to -COCl formation that was used to immobilize the decorated magnetic nanoparticles. The method developed in this study can provide a reference for many surface or interfacial studies important for selective attachment of adsorbed organic or inorganic materials or particles.