19F NMR Probes: Molecular Logic Material Implications for the Anion Discrimination and Chemodosimetric Approach for Selective Detection of H2O2.

Detection and discrimination of similar solvation energies of bioanalytes are vital in medical and practical applications. Currently, various advanced techniques are equipped to recognize these crucial bioanalytes. Each strategy has its own benefits and limitations. One-dimensional response, lack of discrimination power for anions, and reactive oxygen species (ROS) generally limit the utilized fluorescent probe. Therefore, a cutting-edge, refined method is expected to conquer these limitations. The use of 19F NMR spectroscopy for detecting and discriminating essential analytes in practical applications is an emerging technique. As an alternative strategy, we report two fluorinated boronic acid-appended pyridinium salts 5-F-o-BBBpy (1) and 5-CF3-o-BBBpy (2). Probe (1) acts as a chemosensor for identifying and discriminating inorganic anions with similar solvation energies with strong bidirectional 19F shifts in the lower ppm range. Probe (2) turns as a chemo dosimeter for the selective detection and precise quantification of hydrogen peroxide (H2O2) among other competing ROS. To demonstrate real-life applicability, we successfully quantified H2O2 via probe (2) in different pharmaceutical, dental, and cosmetic samples. We found that tuning the -F/-CF3 moiety to the arene boronic acid enables the π-conjugation, a crucial prerequisite for the discrimination of anions and H2O2. Characteristic 19F NMR fingerprints in the presence of anions revealed a complementary implication (IMP)/not implication (NIMP) logic function. Finally, the 16 distinct binary Boolean operations on two logic values are defined for "functional completeness" using the special property of the IMP gate. Boolean logic's ability to handle information by utilizing characteristic 19F NMR fingerprints has not been seen previously in a single chemical platform for detecting and differentiating such anions.

Quantifying CO-release from a photo-CORM using 19F NMR: An investigation into light-induced CO delivery.

Carbon monoxide (CO) is an innate signaling molecule that can regulate immune responses and interact with crucial elements of the circadian clock. Moreover, pharmacologically, CO has been substantiated for its therapeutic advantages in animal models of diverse pathological conditions. Given that an excessive level of CO can be toxic, it is imperative to quantify the necessary amount for therapeutic use accurately. However, estimating gaseous CO is notably challenging. Therefore, novel techniques are essential to quantify CO in therapeutic applications and overcome this obstacle precisely. The classical Myoglobin (Mb) assay technique has been extensively used to determine the amount of CO-release from CO-releasing molecules (CORMs) within therapeutic contexts. Nevertheless, specific challenges arise when applying the Mb assay to evaluate CORMs featuring innovative molecular architectures. Here, we report a fluorinated photo-CORM (CORM-FBS) for the photo-induced CO-release. We employed the 19F NMR spectroscopy approach to monitor the release of CO as well as quantitative evaluation of CO release. This new 19F NMR approach opens immense opportunities for researchers to develop reliable techniques for identifying molecular structures, quantitative studies of drug metabolism, and monitoring the reaction process.

TiO2 supported pallidum-bipyridyl complex as an efficient catalyst for Suzuki-Miyaura reaction in aqueous-ethanol.

Owing to their improved catalytic stability and ability to undergo repeated cycles, solid-supported catalysts show great potential for various catalytic reactions. In this study, we synthesized a catalyst comprising a palladium-2,2-bipyridine complex supported on TiO2 nanoparticles (TiO2@BDP-PdCl2) fully characterised and investigated its efficacy in Suzuki-Miyaura cross coupling reactions involving phenyl boronic acid with various aryl halides under mild reaction conditions. The 2,2'- bipyridine (bp) has shown excellent complexation properties for Pd (II) and it could be easily anchored onto functionalized TiO2 support by the bridging carboxylate ions. The composition and structure of the as-prepared catalyst was characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Transmission Electron Microscope (TEM), X-ray photoelectron spectroscopy (XPS), and UV-Vis spectroscopy. The catalyst easily demonstrated separability, enhancing its practicality in catalytic processes. Subsequent utilization showed a consistent activity level, suggesting the stabilization of the aggregated catalyst species. This research sheds light on the importance of catalyst stability and maintenance during consecutive reaction cycles.

Lysosome targeted visible light-induced photo-CORM for simultaneous CO-release and singlet oxygen generation.

We report a specific lysosome targeted light-responsive CO-releasing molecule (Lyso-CORM). Lyso-CORM is very stable under dark conditions. CO and singlet oxygen (1O2) generation was effectively triggered under one photon and two photon excitation (800 nm) conditions. The cytotoxicity results demonstrated that Lyso-CORM showed good phototoxicity due to the synergistic effect of CO and 1O2 release, and its good biocompatibility, negligible dark toxicity and specific lysosome targeting make Lyso-CORM a potent candidate for phototherapeutic applications.

Recent Advances in Drug Release, Sensing, and Cellular Uptake of Ring-Opening Metathesis Polymerization (ROMP) Derived Poly(olefins).

The synthesis and applications of ring-opening metathesis polymerization (ROMP) derived poly(olefins) have emerged as an exciting area of great interest in the field of biomaterials science. The major focus of this mini-review is to present recent advances in the synthesis of functional materials using ROMP-derived poly(olefins) utilized for drug release, sensing, and cellular uptake in the past seven years (2015-2022). This review reveals that materials synthesized by ROMP-derived well-defined functional poly(olefins) stand to be highly promising systems for medical as well as biological studies. Thus, this review may prove to be beneficial for the design and development of new smart and flexible-functionality ROMP-based polymeric materials for various biological applications.

Multifunctional rhodamine B appended ROMP derived fluorescent probe detects Al3+ and selectively labels lysosomes in live cells.

There a few reports of rhodamine-based fluorescent sensors for selective detection of only Al3+, due to the challenge of identifying a suitable ligand for binding Al3+ ion. The use of fluorophore moieties appended to a polymer backbone for sensing applications is far from mature. Here, we report a new fluorescent probe/monomer 4 and its ROMP derived polymer P for specific detection of Al3+ ions. Both monomer 4 and its polymer P exhibit high selectivity toward only Al3+ with no interference from other metal ions, having a limit detection of 0.5 and 2.1 µM, respectively. The reversible recognition of monomer 4 and P for Al3+ was also proved in presence of Na2EDTA by both UV-Vis and fluorometric titration. The experimental data indicates the behavior of 4 and P toward Al3+ is pH independent in medium conditions. In addition, the switch-on luminescence response of 4 at acidic pH (0 < 5.0), allowed us to specifically stain lysosomes (pH ~ 4.5-5.0) in live cells.

Green Light-Responsive CO-Releasing Polymeric Materials Derived from Ring-Opening Metathesis Polymerization.

Carbon monoxide (CO) is an important biological gasotransmitter in living cells. Precise spatial and temporal control over release of CO is a major requirement for clinical application. To date, the most reported carbon monoxide releasing materials use expensive fabrication methods and require harmful and poorly designed tissue-penetrating UV irradiation to initiate the CO release precisely at infected sites. Herein, we report the first example of utilizing a green light-responsive CO-releasing polymer P synthesized via ring-opening metathesis polymerization. Both monomer M and polymer P were very stable under dark conditions and CO release was effectively triggered using minimal power and low energy wavelength irradiation (550 nm, ≤28 mW). Time-dependent density functional theory (TD-DFT) calculations were carried out to simulate the electronic transition and insight into the nature of the excitations for both L and M. TD-DFT calculations indicate that the absorption peak of M is mainly due to the excitation of the seventh singlet excited state, S7. Furthermore, stretchable materials using polytetrafluoroethylene (PTFE) strips based on P were fabricated to afford P-PTFE, which can be used as a simple, inexpensive, and portable CO storage bandage. Insignificant cytotoxicity as well as cell permeability was found for M and P against human embryonic kidney cells.