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.

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.

Fluorescence of the Retinal Chromophore in Microbial and Animal Rhodopsins.

Fluorescence of the vast majority of natural opsin-based photoactive proteins is extremely low, in accordance with their functions that depend on efficient transduction of absorbed light energy. However, several recently proposed classes of engineered rhodopsins with enhanced fluorescence, along with the discovery of a new natural highly fluorescent rhodopsin, NeoR, opened a way to exploit these transmembrane proteins as fluorescent sensors and draw more attention to studies on this untypical rhodopsin property. Here, we review the available data on the fluorescence of the retinal chromophore in microbial and animal rhodopsins and their photocycle intermediates, as well as different isomers of the protonated retinal Schiff base in various solvents and the gas phase.

Simultaneous Catechol and Hydroquinone Detection with Laser Fabricated MOF-Derived Cu-CuO@C Composite Electrochemical Sensor.

The conversion of metal-organic frameworks (MOFs) into advanced functional materials offers a promising route for producing unique nanomaterials. MOF-derived systems have the potential to overcome the drawbacks of MOFs, such as low electrical conductivity and poor structural stability, which have hindered their real-world applications in certain cases. In this study, laser scribing was used for pyrolysis of a Cu-based MOF ([Cu{1,4-CH(COO)}(4,4'-bipy)]) to synthesize a Cu-CuO@C composite on the surface of a screen-printed electrode (SPE).

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.

Femtosecond Laser-Printed Gold Nanoantennas for Electrically Driven and Bias-Tuned Nanoscale Light Sources Operating in Visible and Infrared Spectral Ranges.

Nanoscale electrically driven light-emitting sources with tunable wavelength represent a milestone for implementation of integrated optoelectronic chips. Plasmonic nanoantennas exhibiting an enhanced local density of optical states (LDOS) and strong Purcell effect hold promise for fabrication of bright nanoscale light emitters. Here, we justify gold parabola-shaped nanobumps and their ordered arrays produced by direct ablation-free femtosecond laser printing as broadband plasmonic light sources electrically excited by a probe of scanning tunneling microscope (STM).

Non-invasive transcutaneous influenza immunization using vaccine-loaded vaterite particles.

Transcutaneous immunization receives much attention due to the recognition of a complex network of immunoregulatory cells in various layers of the skin. The elaboration of non-invasive needle-free approaches towards antigen delivery holds especially great potential here while searching for a hygienically optimal vaccination strategy. Here, we report on a novel protocol for transfollicular immunization aiming at delivery of an inactivated influenza vaccine to perifollicular antigen presenting cells without disrupting the stratum corneum integrity.

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.

Fluorescence Imaging of Cell Membrane Potential: From Relative Changes to Absolute Values.

Membrane potential is a fundamental property of biological cells. Changes in membrane potential characterize a vast number of vital biological processes, such as the activity of neurons and cardiomyocytes, tumorogenesis, cell-cycle progression, etc. A common strategy to record membrane potential changes that occur in the process of interest is to utilize organic dyes or genetically-encoded voltage indicators with voltage-dependent fluorescence.

Nanoscale Electric Field Probing in a Single Nanowire with Raman Spectroscopy and Elastic Strain.

In this work we investigate the Raman response of extremely strained gallium phosphide nanowires. We analyze new strain-induced spectral phenomena such as 2-fold and 3-fold phonon peak splitting which arise due to nontrivial internal electric field distribution coupled with inhomogeneous strain. We show that high bending strain acts as a probe allowing us to define the electric field distribution with deep subwavelength resolution using the corresponding changes of the Raman spectra.

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.

Tuning the Optical Properties and Conductivity of Bundles in Networks of Single-Walled Carbon Nanotubes.

The films of single-walled carbon nanotubes (SWCNTs) are a promising material for flexible transparent electrodes, which performance depends not only on the properties of individual nanotubes but also, foremost, on bundling of individual nanotubes. This work investigates the impact of densification on optical and electronic properties of SWCNT bundles and fabricated films. Our ab initio analysis shows that the optimally densified bundles, consisting of a mixture of quasi-metallic and semiconducting SWCNTs, demonstrate quasi-metallic behavior and can be considered as an effective conducting medium.

Lanthanide-Ion-Doping Effect on the Morphology and the Structure of NaYF:Ln Nanoparticles.

Two series of β-NaYF:Ln nanoparticles (Ln = La-Nd, Sm-Lu) containing 20 at. % and 40 at. % of Ln with well-defined morphology and size were synthesized via a facile citric-acid-assisted hydrothermal method using rare-earth chlorides as the precursors.

Copper-Ruthenium Composite as Perspective Material for Bioelectrodes: Laser-Assisted Synthesis, Biocompatibility Study, and an Impedance-Based Cellular Biosensor as Proof of Concept.

Copper is an inexpensive material that has found wide application in electronics due to its remarkable electric properties. However, the high toxicity of both copper and copper oxide imposes restrictions on the application of this metal as a material for bioelectronics. One way to increase the biocompatibility of pure copper while keeping its remarkable properties is to use copper-based composites.

Study of Cryogenic Unmasked Etching of "Black Silicon" with Ar Gas Additives.

The influence of Ar gas additives on ≪black silicon≫ formation is shown in this work. The way to achieve the conical shape of Si texture using low Ar dilution is demonstrated. Also, a possibility of silicon nanowire width reduction keeping a high density of array is shown.

Azobenzene/Tetraethyl Ammonium Photochromic Potassium Channel Blockers: Scope and Limitations for Design of Para-Substituted Derivatives with Specific Absorption Band Maxima and Thermal Isomerization Rate.

Azobenzene/tetraethyl ammonium photochromic ligands (ATPLs) are photoactive compounds with a large variety of photopharmacological applications such as nociception control or vision restoration. Absorption band maximum and lifetime of the less stable isomer are important characteristics that determine the applicability of ATPLs. Substituents allow to adjust these characteristics in a range limited by the azobenzene/tetraethyl ammonium scaffold.

Flexible Perovskite CsPbBr Light Emitting Devices Integrated with GaP Nanowire Arrays in Highly Transparent and Durable Functionalized Silicones.

The architecture of transparent contacts is of utmost importance for creation of efficient flexible light-emitting devices (LEDs) and other deformable electronic devices. We successfully combined the newly synthesized transparent and durable silicone rubbers and the semiconductor materials with original fabrication methods to design LEDs and demonstrate their significant flexibility. We developed electrodes based on a composite GaP nanowire-phenylethyl-functionalized silicone rubber membrane, improved with single-walled carbon nanotube films for a hybrid poly(ethylene oxide)-metal-halide perovskite (CsPbBr) flexible green LED.

Heterocycloalkynes Fused to a Heterocyclic Core: Searching for an Island with Optimal Stability-Reactivity Balance.

In the search for fundamentally new, active, stable, and readily synthetically accessible cycloalkynes as strain-promoted azide-alkyne cycloaddition (SPAAC) reagents for bioorthogonal bioconjugation, we integrated two common approaches: the reagent destabilization by the increase of a ring strain and the transition state stabilization through electronic effects. As a result new SPAAC reagents, heterocyclononynes fused to a heterocyclic core, were created. These compounds can be obtained through a general synthetic route based on four crucial steps: the electrophile-promoted cyclization, Sonogashira coupling, Nicholas reaction, and final deprotection of Co-complexes of cycloalkynes from cobalt.

Ultrasound-Assisted Synthesis of Luminescent Micro- and Nanocrystalline Eu-Based MOFs as Luminescent Probes for Heavy Metal Ions.

The luminescent coarse-, micro- and nanocrystalline europium(III) terephthalate tetrahydrate (Eubdc·4HO) metal-organic frameworks were synthesized by the ultrasound-assisted wet-chemical method. Electron micrographs show that the europium(III) terephthalate microparticles are 7 μm long leaf-like plates. According to the dynamic light scattering technique, the average size of the Eubdc·4HO nanoparticles is equal to about 8 ± 2 nm.

Free Energy Computation for an Isomerizing Chromophore in a Molecular Cavity via the Average Solvent Electrostatic Configuration Model: Applications in Rhodopsin and Rhodopsin-Mimicking Systems.

We present a novel technique for computing the free energy differences between two chromophore "isomers" hosted in a molecular environment (a generalized solvent). Such an environment may range from a relatively rigid protein cavity to a flexible solvent environment. The technique is characterized by the application of the previously reported "average electrostatic solvent configuration" method, and it is based on the idea of using the free energy perturbation theory along with a chromophore annihilation procedure in thermodynamic cycle calculations.

Laser-Assisted Surface Modification of Ni Microstructures with Au and Pt toward Cell Biocompatibility and High Enzyme-Free Glucose Sensing.

We investigated the influence of morphology of Ni microstructures modified with Au and Pt on their cell biocompatibility and electrocatalytic activity toward non-enzymatic glucose detection. Synthesis and modification were carried out using a simple and inexpensive approach based on the method of laser-induced deposition of metal microstructures from a solution on the surface of various dielectrics. Morphological analysis of the fabricated materials demonstrated that the surface of the Ni electrode has a hierarchical structure with large-scale 10 μm pores and small-scale 10 nm irregularities.

Ultrafast Excited-State Dynamics of CuBr Complex Studied with Sub-20 fs Resolution.

Ultrafast excited-state dynamics of CuBr complex was studied in acetonitrile and dichloromethane solutions using femtosecond transient absorption spectroscopy with 18 fs temporal resolution and quantum-chemical DFT calculations. Upon 640 nm excitation, the CuBr complex is promoted to the ligand-to-metal charge transfer (LMCT) state, which then shortly undergoes internal conversion into the vibrationally hot ligand field (LF) excited state with time constants of 30 and 40 fs in acetonitrile and dichloromethane, respectively. The LF state nonradiatively relaxes into the ground state in 2.

Simple Models to Study Spectral Properties of Microbial and Animal Rhodopsins: Evaluation of the Electrostatic Effect of Charged and Polar Residues on the First Absorption Band Maxima.

A typical feature of proteins from the rhodopsin family is the sensitivity of their absorption band maximum to protein amino acid composition. For this reason, studies of these proteins often require methodologies that determine spectral shift caused by amino acid substitutions. Generally, quantum mechanics/molecular mechanics models allow for the calculation of a substitution-induced spectral shift with high accuracy, but their application is not always easy and requires special knowledge.