Boltzmann-Distribution-Driven Cathodoluminescence Thermometry in Transmission Electron Microscopy.

Nanothermometry in transmission electron microscopy (TEM) is useful for comprehending the functioning mechanisms of the heterogeneous matter through real-time observations. Herein, we introduce a Boltzmann-distribution-driven cathodoluminescence (CL) nanothermometry for local temperature probing in TEM. The population distribution across the close-lying Stark sublevels of dysprosium ions in an yttrium vanadate matrix follows the Boltzmann distribution, enabling the use of the CL-intensity ratio as a thermometry over a wide temperature range of 103-435 K with a relative sensitivity exceeding 3% K and precision of ±2%.

Smart photopharmacological agents: LaVO:Eu@vinyl phosphonate combining luminescence imaging and photoswitchable butyrylcholinesterase inhibition.

The combination of photoswitchability and bioactivity in one compound provides interesting opportunities for photopharmacology. Here, we report a hybrid compound that in addition allows for its visual localization. It is the first demonstration of its kind and it even shows high photoswitchability.

The Structure and Optical Properties of Luminescent Europium Terephthalate Antenna Metal-Organic Frameworks Doped by Yttrium, Gadolinium, and Lanthanum Ions.

New heterometallic antenna terephthalate MOFs, namely, (EuM)bdc·4HO (M = Y, La, Gd) (x = 0.001-1), were synthesized by a one-step method from aqueous solutions. The resulting compounds are isomorphic to each other; the crystalline phase corresponds to Lnbdc∙4HO.

Iridium(III)-Incorporating Self-Healing Polysiloxanes as Materials for Light-Emitting Oxygen Sensors.

Polymer-metal complexes (PMCs) based on poly(2,2'-bipyridine-4,4'-dicarboxamide-co-polydimethylsiloxanes) with cyclometalated di(2-phenylpyridinato-C,N')iridium(III) fragments and cross-linked by Zn (Zn[Ir]-BipyPDMSs) or Ir (Ir[Ir]-BipyPDMSs) represent flexible, stretchable, phosphorescent, and self-healing molecular oxygen sensors. PMCs provide strong phosphorescence at λ = 595-605 nm. Zn[Ir]-BipyPDMS with PDMS chain length of M = 5000 has the highest quantum yield of 9.

Remote temperature sensing in microelectronics: optical thermometry using dual-center phosphors.

Remote thermal sensing has emerged as a temperature detection technique for tasks in which standard contact thermometers cannot be used due to environment or dimension limitations. One of such challenging tasks is the measurement of temperature in microelectronics. Here, optical thermometry using co-doped and mixed dual-center GdO:Tb/Eusamples were realized.

Nanoscale Cathodoluminescence Thermometry with a Lanthanide-Doped Heavy-Metal Oxide in Transmission Electron Microscopy.

When navigated by the available energy of a system, often provided in the form of heat, physical processes or chemical reactions fleet on a free-energy landscape, thus changing the structure. In transmission electron microscopy (TEM), where material structures are measured and manipulated inside the microscope while being subjected to external stimuli such as electrical fields, laser irradiation, or mechanical stress, it is necessary to precisely determine the local temperature of the specimen to provide a comprehensive understanding of material behavior and to establish the relationship among energy, structure, and properties at the nanoscale. Here, we propose using cathodoluminescence (CL) spectroscopy in TEM for measurement of the local temperature.

Microcrystalline Luminescent (EuLn)bdc·nHO (Ln = La, Gd, Lu) Antenna MOFs: Effect of Dopant Content on Structure, Particle Morphology, and Luminescent Properties.

In this work, three series of micro-sized heterometallic europium-containing terephthalate MOFs, (EuLn)bdc·nHO (Ln = La, Gd, Lu), are synthesized via an ultrasound-assisted method in an aqueous medium. La and Gd-doped terephthalates are isostructural to Eubdc·4HO. Lu-doped compounds are isostructural to Eubdc·4HO with Lu contents lower than 95 at.

Design of luminescent complexes with different CuI cores based on pyridyl phenoxarsines.

A series of luminescent CuI clusters with stair-step, cubane, and octahedral geometries supported by a novel type of cyclic As,N-ligand, pyridyl-containing 10-phenoxarsines, were synthesized and characterized by NMR spectroscopy, mass spectrometry, elemental analysis, and single-crystal X-ray diffraction analysis. An unusual arrangement of As,N-bidentate and μ-iodo ligands was found in the octahedral cluster. The structural diversity of the Cu(I) complexes is reflected in their photophysical properties: the phosphorescence spectra of the compounds display emission in a broad spectral range of 495-597 nm.

Linkage of the Dinuclear Gold(I) Complex Luminescence and Origin of Endocyclic Amino Group of Cyclic PN-Bridging Ligands.

Gold(I) complexes of LAuCl composition based on PN ligands, namely 1,5-diaza-3,7-diphosphacyclooctanes, containing ethylpyridyl substituents at the phosphorus atoms and sp- or sp-hybridized endocyclic nitrogen atoms were synthesized. The SCXRD analysis indicated the strong impact of the geometry of the nitrogen atom on the structure and conformational flexibility of the complexes. The -aryl substituted ligand with the planar endocyclic nitrogen atom provides higher flexibility of the complex and an ability to bind the solvent molecules in the "host-guest" mode, whereas that kind of behavior is forbidden for the complex with an -alkyl substituted ligand with a pyramidal nitrogen atom.

All-in-One Photoactivated Inhibition of Butyrylcholinesterase Combined with Luminescence as an Activation and Localization Indicator: Carbon Quantum Dots@Phosphonate Hybrids.

Photopharmacology is a booming research area requiring a new generation of agents possessing simultaneous functions of photoswitching and pharmacophore. It is important that any practical implementation of photopharmacology ideally requires spatial control of the medicinal treatment zone. Thus, advances in the study of substances meeting all the listed requirements will lead to breakthrough research in the coming years.

Silver nanoparticle-based SERS sensors for sensitive detection of amyloid-β aggregates in biological fluids.

One of the hallmarks of Alzheimer's disease (AD) pathogenesis is the production, aggregation, and deposition of amyloid-β (Aβ) peptide. Surface-enhanced Raman spectroscopy (SERS) is a promising analytical technique capable of providing valuable information on chemical composition and molecule conformations in biological samples. However, one of the main challenges for introducing the SERS technique into the practice is preparation of scalable and at the same time stable nanostructured sensors with uniform spatial distribution of nanoparticles.

Development of Fluorescent Isocoumarin-Fused Oxacyclononyne - 1,2,3-Triazole Pairs.

Fluorescent isocoumarin-fused cycloalkynes, which are reactive in SPAAC and give fluorescent triazoles regardless of the azide nature, have been developed. The key structural feature that converts the non-fluorescent cycloalkyne/triazole pair to its fluorescent counterpart is the pi-acceptor group (COOMe, CN) at the C6 position of the isocoumarin ring. The design of the fluorescent cycloalkyne/triazole pairs is based on the theoretical study of the S1 state deactivation mechanism of the non-fluorescent isocoumarin-fused cycloalkyne IC9O using multi-configurational ab initio and DFT methodologies.

3D Nanocomposite with High Aspect Ratio Based on Polyaniline Decorated with Silver NPs: Synthesis and Application as Electrochemical Glucose Sensor.

In this paper, we present a new methodology for creating 3D ordered porous nanocomposites based on anodic aluminum oxide template with polyaniline (PANI) and silver NPs. The approach includes in situ synthesis of polyaniline on templates of anodic aluminum oxide nanomembranes and laser-induced deposition (LID) of Ag NPs directly on the pore walls. The proposed method allows for the formation of structures with a high aspect ratio of the pores, topological ordering and uniformity of properties throughout the sample, and a high specific surface area.

Effect of Gd, La, Lu Co-Doping on the Morphology and Luminescent Properties of NaYF:Sm Phosphors.

The series of luminescent NaYF:Sm nano- and microcrystalline materials co-doped by La, Gd, and Lu ions were synthesized by hydrothermal method using rare earth chlorides as the precursors and citric acid as a stabilizing agent. The phase composition of synthesized compounds was studied by PXRD. All synthesized materials except ones with high La content (where LaF is formed) have a β-NaYF crystalline phase.

Brightly Luminescent (TbLu)bdc·nHO MOFs: Effect of Synthesis Conditions on Structure and Luminescent Properties.

Luminescent, heterometallic terbium(III)-lutetium(III) terephthalate metal-organic frameworks (MOFs) were synthesized via direct reaction between aqueous solutions of disodium terephthalate and nitrates of corresponding lanthanides by using two methods: synthesis from diluted and concentrated solutions. For (TbLu)bdc·nHO MOFs (bdc = 1,4-benzenedicarboxylate) containing more than 30 at. % of Tb, only one crystalline phase was formed: Lnbdc·4HO.

ZnTe Crystal Multimode Cryogenic Thermometry Using Raman and Luminescence Spectroscopy.

In this study, ZnTe crystal was applied to provide precise thermal sensing for cryogenic temperatures. Multiple techniques, namely Raman and photoluminescence spectroscopies, were used to broaden the operating temperature range and improve the reliability of the proposed thermometers. Raman-based temperature sensing could be applied in the range of 20-100 K, while luminescence-based thermometry could be utilized in a narrower range of 20-70 K.

Green Emissive Copper(I) Coordination Polymer Supported by the Diethylpyridylphosphine Ligand as a Luminescent Sensor for Overheating Processes.

Tertiary diethylpyridylphosphine was synthesized by the reaction of pyridylphosphine with bromoethane in a suberbasic medium. The reaction of phosphine with the copper(I) iodide led to the formation of a copper(I) coordination polymer, which, according to the X-ray diffraction data, has an intermediate structure with a copper-halide core between the octahedral and stairstep geometries of the CuI clusters. The obtained coordination polymer exhibits a green emission in the solid state, which is caused by the (M+X)LCT transitions.

Laser-Induced Synthesis of Electrocatalytically Active Ag, Pt, and AgPt/Polyaniline Nanocomposites for Hydrogen Evolution Reactions.

We present an efficient and easily implemented approach for creating stable electrocatalytically active nanocomposites based on polyaniline (PANI) with metal NPs. The approach combines in situ synthesis of polyaniline followed by laser-induced deposition (LID) of Ag, Pt, and AgPt NPs. The observed peculiarity of LID of PANI is the role of the substrate during the formation of multi-metallic nanoparticles (MNP).

Near-Infrared Emission of HgTe Nanoplatelets Tuned by Pb-Doping.

Doping the semiconductor nanocrystals is one of the most effective ways to obtain unique materials suitable for high-performance next-generation optoelectronic devices. In this study, we demonstrate a novel nanomaterial for the near-infrared spectral region. To do this, we developed a partial cation exchange reaction on the HgTe nanoplatelets, substituting Hg cations with Pb cations.

Emission and Luminescent Vapochromism Control of Octahedral Cu I Complexes by Conformationally Restricted P,N Ligands.

A conformationally restricted P,N-ligand capable of the design of polynuclear copper(I) complexes was synthesized via the reaction of primary pyridylphosphine, paraformaldehyde, and benzhydrylamine. The reaction of the ligand with copper(I) iodide leads to the tetranuclear copper(I) complex with the octahedral type of copper-iodide core. Different orientation of coordination bonds of the ligands relative to the P,N -heterocyclic fragments and to the Cu I cores leads to the existence of two types of conformers of the complex with "compact" or "stretched" geometry of the Cu I cluster.

Low-doped LaVO:Eu phosphor for multimode optical thermal sensing.

In the last decade much attention has been paid to the development of novel approaches in luminescence thermometry, which could allow contactless and noninvasive temperature sensing when traditional thermometers are useless. Typically, an optical thermometer exploits a distinct luminescence parameter to define temperature. However, the use of multimode sensors can significantly broaden the working range and improve the reliability of the temperature measurements.

Ratiometric thermometry using single Er-doped CaWOphosphors.

Single doped CaWO:Erphosphors were synthesized and studied for application of optical thermal sensing within a wide range of 98-773 K. Ratiometric strategy utilizing two luminescence intensity ratios, one between host and Erband (LIR) and second between different Ertransitions (LIR), results in self-referencing temperature readouts. The presence of two temperature-dependent parameters could improve thermometric characteristics and broaden the working temperature range compared to a usual single-parameter thermometer.

Deep-Blue Emissive Copper(I) Complexes Based on P-Thiophenylethyl-Substituted Cyclic Bisphosphines Displaying Photoinduced Structural Transformations of the Excited States.

A synthetic method for a primary 2-(thiophen-2'-yl)ethylphosphine was developed. The reaction of thiophenylethylphosphine with paraformaldehyde and primary arylamines leads to the formation of cyclic bisphosphines, namely, 1,5-di(aryl)-3,7-bis(thiophenylethyl)-1,5-diaza-3,7-diphosphacyclooctane (aryl = phenyl, -tolyl). The obtained bisphosphines form cationic bis-P,P-chelate complexes with copper(I) tetrafluoroborate, which were structurally characterized by NMR spectroscopy, mass spectrometry, and elemental and XRD analyses.

Heterometallic Europium(III)-Lutetium(III) Terephthalates as Bright Luminescent Antenna MOFs.

A new series of luminescent heterometallic europium(III)-lutetium(III) terephthalate metal-organic frameworks, namely (EuLu)bdc·nHO, was synthesized using a direct reaction in a water solution. At the Eu concentration of 1-40 at %, the MOFs were formed as a binary mixture of the (EuLu)bdc and (EuLu)bdc·4HO crystalline phases, where the Lnbdc·4HO crystalline phase was enriched by europium(III) ions. At an Eu concentration of more than 40 at %, only one crystalline phase was formed: (EuLu)bdc·4HO.

Photoswitchable Phosphonate-Fullerene Hybrids with Cholinesterase Activity.

Modern progress in photopharmocology calls for new generation of compounds joining bioactivity, photoswitchable properties and high selectivity of response to light wavelength. Introduced here, phosphonate-fullerene hybrids are the first representatives of such compounds. Phosphonate-fullerene hybrids were synthesized on a base of fullerene C and organophosphates with the function of photoswitchable cholinesterase activity-phosphorylated thiazolotriazole and aminomalonate compounds and studied with FTIR, UV-VIS spectroscopy and IPC-micro neurotoxin amperometric analysis.