Toward Upconversion (Yb-Er) and near-Infrared (Yb-Ho-Er, Nd-Yb) Thermometry with Sea Urchin Type GdPO Nanoarchitectures.

In recent years, optical temperature probes operating in the second near-infrared (BW-II) and third near-infrared (BW-III) biological windows have garnered significant attention in the scientific community. For biological applications these probes offer distinct advantages, including enhanced tissue penetration depth, minimal autofluorescence, and a remarkable improvement in imaging sensitivity and spatial resolution. Moving toward theranostic applications, there is a growing demand for the development of materials that integrate both BW-II and BW-III thermometry systems with drug delivery functionalities.

Exploring the potential of lanthanide-doped oxyfluoride materials for bright green upconversion and their promising applications towards temperature sensing and drug delivery.

The most efficient upconversion (UC) materials reported to date are based on fluoride hosts with low phonon energies, which reduce the amount of nonradiative transitions. In particular, NaYF doped with Yb and Er at appropriate ratios is known as one of the most efficient UC phosphors. However, its low thermal stability limits its use for certain applications.

Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material.

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network.

Ratiometric dual-emitting thermometers based on rhodamine B dye-incorporated (nano) curcumin periodic mesoporous organosilicas for bioapplications.

This study explores the potential of combining periodic mesoporous organosilicas (PMOs) with a fluorescent dye to develop a ratiometric thermometry system with enhanced stability, sensitivity, and biocompatibility. PMOs, ordered porous materials known for their stability and versatility, serve as an ideal platform. Curcumin, a natural polyphenol and fluorescent dye, is incorporated into PMOs to develop curcumin-functionalized PMOs (C-PMO) and curcumin-pyrazole-functionalized PMOs (CP-PMO) hydrolysis and co-condensation.

Single-Crystal-to-Single-Crystal Photosynthesis of Supramolecular Organoboron Polymers with Dynamic Effects.

The solid-state synthesis of single-crystalline organic polymers, having functional properties, remains an attractive and developing research area in polymer chemistry and materials science. However, light-triggered topochemical synthesis of crystalline polymers comprising an organoboron backbone has not yet been reported. Here, we describe an intriguing example of single-crystal-to-single-crystal (SCSC) rapid photosynthesis (occurs on a seconds-scale) of two structurally different linear organoboron polymers, driven by environmentally sustainable visible/sun light, obtained from the same monomer molecule.

Versatile Palladium-catalyzed intramolecular cyclization to access new luminescent azaphosphaphenalene motifs.

Using a straightforward sequence of diphosphonylation and a Pd-catalysed concerted-metalation-deprotonation (CMD), a synthetic strategy towards polyaromatic phosphorus containing heterocycles was developed. Herein, we report the synthesis and characterization of new azaphosphaphenalenes, using easily accessible palladium catalysts and starting materials. The key tetrahydroquinoline intermediates of the reaction were synthesised via a fast and effective procedure and could be isolated as such, or further reacted towards the target polyaromatic structures.

Lanthanide-grafted hollow bipyridine-based periodic mesoporous organosilicas as chemical sensors.

We have synthesized a co-condensed hollow ethane-bipyridine periodic mesoporous organosilica (HEt-bpy-PMO) as a host material to anchor lanthanides for the purpose of developing a multifunctional chemical sensor. The host material was grafted with lanthanide chloride salts or complexes. The luminescence properties of the developed series of hybrid materials were studied in detail in the solid-state and after dispersing in water.

Turning 3D Covalent Organic Frameworks into Luminescent Ratiometric Temperature Sensors.

In this study, we report hybrid crystalline lanthanide-containing 3D covalent organic framework (Ln@3D COF) materials that are suitable for temperature sensing applications. Different routes to obtain these hybrid materials were tested and compared for material quality and thermometric properties. In the first approach, a bipyridine-containing 3D COF (Bipy COF) was grafted with a range of visible emitting lanthanide (Eu, Tb, Dy, and Eu/Tb) β-diketonate complexes.

Visible Light-fueled Mechanical Motions with Dynamic Phosphorescence Induced by Topochemical [2+2] Reactions in Organoboron Crystals.

In the quest for essential energy solutions towards an ecological friendly future, the transformation of visible light/solar energy into mechanical motions in metal-free luminescent crystals offers a sustainable choice of smart materials for lightweight actuating, and all-organic electronic devices. Such green energy-triggered photodynamic motions with room temperature phosphorescence (RTP) emission in molecular crystals have not been reported yet. Here, we demonstrate three new stoichiometrically different Lewis acid-base molecular organoboron crystals (PS1, PS2, and PS3), which exhibit rapid photosalient effects (ballistic splitting, moving, and jumping) under both ultraviolet (UV) and visible light associated with quantitative single-crystal-to-single-crystal (SCSC) [2+2] cycloaddition of preorganized olefins.

Dual-mode vehicles with simultaneous thermometry and drug release properties based on hollow YO:Er,Yb and YOSO:Er,Yb spheres.

Employing luminescence thermometry in the biomedical field is undeniably appealing as many health conditions are accompanied by temperature changes. In this work, we show our ongoing efforts and results at designing novel vehicles for dual-mode thermometry and pH-dependent drug release based on hollow spheres. Hereby for that purpose, we exploit the hollow YO and YOSO host materials.

Photomechanical Motions in Organoboron-Based Phosphorescent Molecular Crystals Driven by a Crystal-State [2 + 2] Cycloaddition Reaction.

Photoluminescent molecular crystals integrated with the ability to transform light energy into macroscopic mechanical motions are a promising choice of materials for both actuating and photonic devices. However, such dynamic photomechanical effects, based on molecular organoboron compounds as well as phosphorescent crystalline materials, are not yet known. Here we present an intriguing example of photomechanical molecular single crystals of a newly synthesized organoboron containing Lewis acid-base molecular adduct (BN1, substituted triphenylboroxine and 1,2-di(4-pyridyl)ethylene) having a capsule shape molecular geometry.

Deformation-induced phosphorescence shift in a 2D elastically flexible organic single crystal: role of chalcogen-centered weak interactions.

Mechanically responsive organic luminescent crystals are one of the promising choices of materials for flexible photonic devices. However, the change in phosphorescence emission as a function of the flexibility of a crystal has never been reported. Our current findings demonstrate two-dimensional (2D) and one-dimensional (1D) macroscopic elastic deformability, under mechanical stress, in elastically flexible single crystals of dibenzothiophene, and its brominated derivative, respectively.

Unravelling the benefits of transition-metal-co-doping in lanthanide upconversion nanoparticles.

Recent advances reveal that upconversion (UC) luminescent materials are highly important not just from a scientific, but also from a future application standpoint. Although significant progress has been made in this field in recent decades, still their versatile applications are hindered by the low upconversion luminescence intensity and low tuneability, which has hampered further implementation in real life applications. We find it highly beneficial to compile a summary of recent relevant literature and propose ways to enhance upconversion efficiency in lanthanide nanomaterials.

Chemical sensors based on periodic mesoporous organosilica @NaYF:Ln nanocomposites.

Here, three unique organic-inorganic hybrid nanocomposite materials prepared by combining NaYF:Yb,Ln (Ln = Er, Tm, Ho) and periodic mesoporous organosilica (PMO) are proposed for both metal ion sensing and solvent sensing. The luminescence properties of the developed hybrid materials, PMO@NaYF:Yb,Ln, were studied in detail in the solid state and after dispersing in water. It is found that PMO@NaYF:Yb,Er showed selective "turn on" luminescence for Hg with the detection limit of 24.

Predictive modelling of TBARS changes in the intramuscular lipid fraction of raw ground pork enriched with plant extracts.

The aim of the study was to develop and compare the predictive models of lipid oxidation in minced raw pork meat enriched with selected plant extracts (allspice, basil, bay leaf, black seed, cardamom, caraway, cloves, garlic, nutmeg, onion, oregano, rosemary and thyme) by investigation TBARS values changes during storage at different temperatures. Meat samples with extract addition were stored under various temperatures (4, 8, 12, 16, and 20°C). TBARS values changes in samples stored at 12°C were used as external validation dataset.

Ratiometric Thermometers Based on Rhodamine B and Fluorescein Dye-Incorporated (Nano) Cyclodextrin Metal-Organic Frameworks.

Macro- and nanosized core, as well as core-shell, γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) have been designed and used as platforms for the encapsulation of dye molecules to develop the first CD-MOF-based ratiometric optical thermometer materials. A novel dye combination was employed for this purpose, ., the duo rhodamine B (RhB) and fluorescein (FL).

The importance, status, and perspectives of hybrid lanthanide-doped upconversion nanothermometers for theranostics.

Theranostics combines diagnostics and therapy in a single multifunctional system. Multifunctional upconversion luminescent lanthanide-doped nanothermometers for theranostic purposes offer non-invasive and sensitive multimodal performance in the biomedical field over traditional temperature measurement methods. Despite existing challenges, various studies on hybrid upconversion nanothermometers show substantial progress for (bio)imaging, temperature sensing, photodynamic and photothermal therapy, as well as drug delivery applications.

Upconverting Er-Yb Inorganic/Covalent Organic Framework Core-Shell Nanoplatforms for Simultaneous Catalysis and Nanothermometry.

Lanthanide-based luminescent nanoparticles that are thermally responsive can be used to probe temperature changes at a nanoscale regime. However, materials that can work as both a nanothermometer and a catalyst are limited. Herein, we show that covalent organic frameworks (COFs), which is an emerging class of porous crystalline materials, can be grown around lanthanide nanoparticles to create unique core-shell nanostructures.

Chemical sensors based on a Eu(iii)-centered periodic mesoporous organosilica hybrid material using picolinic acid as an efficient secondary ligand.

Through a series of post synthetic modification methods applied to the 100% trans ethenylene-bridged Periodic Mesoporous Organosilica (ePMO), the lanthanide-functionalized hybrid nanomaterial ePMO@Eu_PA (PA = picolinic acid) has been prepared. The pristine and lanthanide-grafted ePMO materials were characterized by powder X-ray diffraction, DRIFTs, TGA, N sorption, SEM and TEM. The selected PA ligand could effectively sensitize the Eu ion, leading to the characteristic luminescence of Eu in ePMO@Eu_PA.

Rational design of lanthanide nano periodic mesoporous organosilicas (Ln-nano-PMOs) for near-infrared emission.

We present three Periodic Mesoporous Organosilica (PMO) materials: a PMO material functionalized with pyridine dicarboxamide (DPA-PMO) and two amine functionalized PMO materials (Am-PMO and Am-ePMO). The pyridine dicarboxamide ligands in the DPA-PMO material provide the tethering sites for Ln3+-coordination. A Schiff base reaction was carried out on the amine functionalized PMOs to introduce similar lanthanide coordination sites.

Overview of N-Rich Antennae Investigated in Lanthanide-Based Temperature Sensing.

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields.

Luminescent PMMA Films and PMMA@SiO Nanoparticles with Embedded Ln Complexes for Highly Sensitive Optical Thermometers in the Physiological Temperature Range*.

In recent years, luminescent materials doped with Ln ions have attracted much attention for their application as optical thermometers based on both downshifting and upconversion processes. This study presents research done on the development of highly sensitive optical thermometers in the physiological temperature range based on poly(methyl methacrylate) (PMMA) films doped with two series of visible Ln complexes (Ln =Tb , Eu , and Sm ) and SiO nanoparticles (NPs) coated with these PMMA films. The best performing PMMA film doped with Tb and Eu complexes was the PMMA[TbEuL tppo]1 film (L =4,4,4-trifluoro-1-phenyl-1,3-butadionate; tppo=triphenylphosphine oxide), which showed good temperature sensing of S =4.

DNA Intercalating Near-Infrared Luminescent Lanthanide Complexes Containing Dipyrido[3,2-:2',3'-]phenazine (dppz) Ligands: Synthesis, Crystal Structures, Stability, Luminescence Properties and CT-DNA Interaction.

In order to create near-infrared (NIR) luminescent lanthanide complexes suitable for DNA-interaction, novel lanthanide dppz complexes with general formula [Ln(NO)(dppz)] (Ln = Nd, Er and Yb; dppz = dipyrido[3,2-:2',3'-]phenazine) were synthesized, characterized and their luminescence properties were investigated. In addition, analogous compounds with other lanthanide ions (Ln = Ce, Pr, Sm, Eu, Tb, Dy, Ho, Tm, Lu) were prepared. All complexes were characterized by IR spectroscopy and elemental analysis.

Luminescent Ratiometric Thermometers Based on a 4f-3d Grafted Covalent Organic Framework to Locally Measure Temperature Gradients During Catalytic Reactions.

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are a new type of support for grafting lanthanide ions (Ln ), which can be employed as ratiometric luminescent thermometers. In this work we have shown that COFs co-grafted with lanthanide ions (Eu , Tb ) and Cu (or potentially other d-metals) can synchronously be employed both as a nanothermometer and catalyst during a chemical reaction. The performance of the thermometer could be tuned by changing the grafted d-metal and solvent environment.

Ho-Yb doped NaGdF nanothermometers emitting in BW-I and BW-II. Insight into the particle growth intermediate steps.

Here, the excellent thermal sensing capability of Ho3+, Yb3+ doped β-NaGdF4 nanoparticles, where the system is excited into the 5F5 ← 5I8 transition of Ho3+ (640 nm), is reported. The ratio of the 2F5/2 → 2F7/2 transition peak of Yb3+ and the 5I6 → 5I8 transition peak of Ho3+ was employed for thermometry applications, resulting in a novel thermometer, which could potentially operate in BW-I and BW-II (BW - biological window). Additionally, interesting findings were made about the influence of the reaction time on the particle morphology and the presence of intermediate morphology forms.