TADF Blue Emitters with Balanced π-Conjugation─Design, Synthesis, Spectral Characterization, and a Model OLED with 8-(5-(tert-Butyl)-1,3,4-oxadiazol-2-yl)-N,N-bis(4-(tert-butyl)phenyl)dibenzo[b,d]furan-2-amine.

Blue organic light-emitting diodes (OLED) suffer from relatively short lifetimes and a comparatively low lighting efficiency. One of the approaches to improving their characteristics is the development of luminophores with the potential for thermally activated delayed fluorescence (TADF). Herein, a set of donor-spacer-acceptor compounds with potential for TADF are designed, synthesized, and computationally and spectroscopically characterized. The excited state dynamics of the most prospective dye is monitored by time-resolved fluorescence and transient absorption spectroscopy. The experimental data are obtained and processed by a newly developed method and supplemented by quantum chemical calculations. The comprehensive approach allowed rationalization of the complex cascade-type photophysical behavior. The most promising emitter is included in an OLED displaying a blue color with a maximum EQE of 4.9% and negligible efficiency roll-off at higher luminance.

Easy and Effective Method for α-CD:N2O Host-Guest Complex Formation.

α-CD:N2O "host-guest" type complexes were formed by a simple solid-gas reaction (N2O sorption into α-CD) under different gas pressures and temperatures. The new N2O inclusion method applied in the present study was compared with the already known technique based on the crystallization of clathrates from a water solution of α-CD saturated with N2O. A maximum storage capacity of 4.5 wt.% N2O was achieved when charging the cyclodextrin from a gas phase. The amount of included gas decreases to 1.3 wt.% when the complex is stored in air at 1 atm and room temperature, analogous to that achieved by the crystallization of α-CD:N2O. Furthermore, it was shown that the external coordination of N2O to either the upper or lower rim of α-CD without hydration water displacement is the preferred mode of binding, due to hydrogen bonds with neighboring -OH groups from the host macrocycle and three of the hydration water molecules nearby. The capacity of α-CD to store N2O and the thermal stability of the α-CD:N2O complex demonstrated promising applications of these types of complexes in food and beverages.

Enhanced Solubility of Ibuprofen by Complexation with ß-Cyclodextrin and Citric Acid.

The ability of ß-CD to form inclusion complexes with ibuprofen (IBU) and at the same time to make a two-phase system with citric acid was explored in the present study for achieving improved solubility and dissolution rate of IBU. Mechanical milling as well as mechanical milling combined with thermal annealing of the powder mixtures were applied as synthetic methods. Solubility and dissolution kinetics of the complexes were studied in compliance with European Pharmacopoeia (ICH Q4B). ß-CD and citric acid (CA) molecules were shown to interact by both ball milling (BM), thermal annealing, as well as BM with subsequent annealing. Complexes were also formed by milling the three compounds (ß-CD, CA and IBU) simultaneously, as well as by a consecutive first including IBU into ß-CD and then binding the formed ß-CD/IBU inclusion complex with CA. As a result, ternary ß-CD/IBU/CA complex formed by initial incorporation of ibuprofen into ß-CD, followed by successive formation of a two-phase mixture with CA, exhibited notably improved dissolution kinetics compared to the pure ibuprofen and slightly better compared to the binary ß-CD/IBU system. Although the addition of CA to ß-CD/IBU does not significantly increase the solubility rate of IBU, it must be considered that the amount of ß-CD is significantly less in the ternary complex compared to the binary ß-CD/IBU.

Luminescence of Binary-Doped Silica Aerogel Powders: A Two-Step Sol-Gel Approach.

In this study, we report a novel synthesis of hydrophobic silica aerogel powder composites, functionalized and binary-doped with [Tb(phen)2](NO3)3 and [Eu(phen)2](NO3)3 nanocrystals, employing a two-step sol-gel methodology. The investigation delves into the structural elucidation, optical properties and thermal conductivity of these functionalized Tb(III)-Eu(III) composites. Our analysis includes diffuse reflectance spectra and excitation and luminescence spectra, highlighting the quantum yields of composites with varying chemical compositions. Remarkably, these samples exhibit a strong luminescence, with distinct hues of red or green based on the specific doping type and level. The detailed examination of excitation spectra and quantum yields establishes robust energy-transfer mechanisms from the 1,10-phenanthroline molecule to the lanthanide ions. Notably, our study uncovers a Tb3⁺→Eu3⁺ energy-transfer phenomenon within the binary functionalized samples, providing compelling evidence for a structural formation process occurring within the mesoporous framework of the aerogel powders.

Determination of N-Acetyl-L-cysteine Ethyl Ester (NACET) by Sequential Injection Analysis.

New sequential injection analysis (SIA) methods with optical sensing for the determination of N-acetyl-L-cysteine ethyl ester (NACET) have been developed and optimized. NACET is a potential drug and antioxidant with advantageous pharmacokinetics. The methods involve the reduction of Cu(II) in its complexes with neocuproine (NCN), bicinchoninic acid (BCA), and bathocuproine disulfonic acid (BCS) to the corresponding chromophoric Cu(I) complexes by the analyte. The absorbance of the Cu(I) complexes with NCN, BCA, and BCS was measured at their maximum absorbance wavelengths of 458, 562, and 483 nm, respectively. The sensing manifold parameters and experimental conditions were optimized for each of the Cu(II) complexes used. Under optimal conditions, the corresponding linear calibration ranges, limits of detection, and sampling rates were 8.0 × 10-6-2.0 × 10-4 mol L-1, 5.5 × 10-6 mol L-1, and 60 h-1 for NCN; 6.0 × 10-6-1.0 × 10-4 mol L-1, 5.2 × 10-6 mol L-1, and 60 h-1 for BCA; and 4.0 × 10-6-1.0 × 10-4 mol L-1, 2.6 × 10-6 mol L-1, and 78 h-1 for BCS. The Cu(II)-BCS complex was found to be best performing in terms of sensitivity and sampling rate. Usual excipients in pharmaceutical preparations did not interfere with NACET analysis.

Silica Gels Doped with Gold Nanoparticles: Preparation, Structure and Optical Properties.

A novel, one-pot sol-gel preparation scheme leading to reproducible incorporation of 20-40 nm sized gold nanoparticles (AuNPs) in SiO2 gels is developed based on in situ reduction during gelation using chloroauric acid and ascorbic acid. Variation in the preparation conditions affects the chemical composition, optical properties and size distribution of the AuNPs incorporated in the silica gels. Different organic dopants, i.e., oleic acid, acetic acid or dodecanethiol, are applied to modify the final composite material and to control the rate of reduction and growth of the AuNPs in the gels. The synthesized samples are characterized by UV/Vis/NIR spectroscopy, X-ray diffraction, transmission electron microscopy, thermal conductivity measurements and DTA/TG measurements. The optical properties of the obtained composites are explained using Mie theory. The incorporation of AuNPs leads to an increase in the thermal conductivity of the silica gels. The best process method in this contribution is the use of NaOH as a gelation catalyst and oleic acid as an organic modifier, leading to 20 nm AuNPs dispersed in the silica matrix.

Facilitated Synthesis of Mg2Ni Based Composites with Attractive Hydrogen Sorption Properties.

Composites based on Mg2Ni with 5% activated carbon from apricot stones (ACAP) have been prepared by ball milling and subsequent annealing in hydrogen atmosphere. The purpose of the primary metal (Mg, Ni, and V) milling was to reduce the particle size and achieve a good contact between them, without forming intermetallic compounds. During hydriding/dehydriding at 300 °C the amount of the Mg2Ni phase progressively increased, and after 10 cycles about 50% Mg2(Ni,V) was achieved. The hydrogenation produced mainly Mg2NiH4, but small amounts of MgH2 and VHx were also detected in the powder mixture. Relatively high hydrogen storage capacity and fast hydriding/dehydriding kinetics of the Mg2.1Ni0.7V0.3-5 wt.% ACAP composite were determined both from hydrogen gas phase and electrochemically.

Hydrogen Gas Phase and Electrochemical Hydriding of LaNi5-xMx (M = Sn, Co, Al) Alloys.

Hydriding/dehydriding properties of a series of LaNi5 based alloys were compared by applying both hydrogen gas phase and electrochemical hydrogen charge/discharge methods. The highest hydrogen absorption capacity of 1.4 wt.% H2 was found for LaNi4.3Co0.4Al0.3, although LaNi4.8Sn0.2 also reveals comparable hydrogen capacity (>1.3%). A significant difference in the hydriding kinetics was observed for all studied alloys before and after activation. The activated alloys (5 cycles at 65 °C, 40 atm. H2) reach their maximum capacities after less than a minute, whereas the pure LaNi5 alloy needs several minutes for complete hydriding. The electrochemical hydriding/dehydriding behavior of the alloys reveals superior performance of LaNi4.3Co0.4Al0.3 and LaNi4.8Sn0.2 compared to the other compositions studied, as the capacity of LaNi4.8Sn0.2 decreases by only 10% for 60 charge/discharge cycles at a current density of 100 mA/g. Good agreement between the hydrogen sorption kinetics of the alloys obtained electrochemically and from hydrogen gas phase has also been observed.

Localization of mercury and gold in cassava (Manihot esculenta Crantz).

The potential of cassava (Manihot esculenta Crantz.) for simultaneous Hg and Au phytoextraction was explored by investigating Hg and Au localization in cassava roots through Micro-Proton Induced X-Ray Emission, High-Resolution Transmission Electron Microscopy (HR-TEM) and X-Ray Diffractometry (XRD). The effect of Hg and Au in the cyanogenic glucoside linamarin distribution was also investigated using Matrix Assisted Laser Desorption Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (MALDI-FT-ICR-MS) imaging. Hg was located mainly in the root vascular bundle of plants grown in 50 or 100 µmol L-1 Hg solutions. Au was localized in the epidermis and cortex or in the epidermis and endodermis for 50 and 100 µmol L-1 Au solutions, respectively. For 50 µmol L-1 solutions of both Hg and Au, the two metals were co-localized in the epidermis. When the Hg concentrations were increased to 100 µmol L-1, Au was still localized to a considerable extent in the epidermis while Hg was located in all root parts. HR-TEM and XRD revealed that Au nanoparticles were formed in cassava roots. MALDI-FT-ICR-MS imaging showed linamarin distribution in the roots of control and plants and metal-exposed plants thus suggesting that linamarin might be involved in Hg and Au uptake and distribution.

The Influence of Preparation Conditions on the Hydrogen Sorption of Mg-Nb2O5-CNT Produced by Ball Milling and Subsequent High-Pressure Torsion.

High energy ball milling and subsequent high-pressure torsion method was carried out on nanocrystalline Mg powders catalyzed by 5 wt.% Nb2O5 and 5 wt.% carbon nanotubes. In the present research two distinct milling routes were performed in order to reveal the influence of the processing conditions on the hydrogenation behavior of the investigated alloys. The hydrogen sorption behavior of the milled powders and the bulk disks was examined in a Sieverts'-type apparatus. Structural characterization of the catalyzed Mg powders and disks has been carried out by high-resolution transmission electron microscopy and X-ray diffraction.

Water inside ß-cyclodextrin cavity: amount, stability and mechanism of binding.

Cyclodextrins (CDs) are native host systems with inherent ability to form inclusion complexes with various molecular entities, mostly hydrophobic substances. Host cyclodextrins are accommodative to water molecules as well and contain water in the native state. For ß-cyclodextrin (ß-CD), there is no consensus regarding the number of bound water molecules and the location of their coordination. A number of intriguing questions remain: (1) Which localities of the host's macrocycle are the strongest attractors for the guest water molecules? (2) What are the stabilizing factors for the water clusters in the interior of ß-CD and what type of interactions between water molecules and cavity walls or between the water molecules themselves are dominating the energetics of the ß-CD hydration? (3) What is the maximum number of water molecules inside the cavity of ß-CD? (4) How do the thermodynamic characteristics of ß-CD hydration compare with those of its smaller α-cyclodextrin (α-CD) counterpart? In this study, we address these questions by employing a combination of experimental (DSC/TG) and theoretical (DFT) approaches.

α-Cyclodextrin: How Effectively Can Its Hydrophobic Cavity Be Hydrated?

Cyclodextrins (CDs) are among the most widely used native host systems with ability to form inclusion complexes with various molecular objects. This ability is so strong that the "hydrophobic" CD cavity never remains empty, even in the guest-free state it is filled with water molecules. However, no consensus has been reached concerning both the total number of hydrating water molecules and their preferred binding location in the CDs. Several outstanding questions regarding the CD hydration still wait to be answered: (1) Which spots of the CD cavity ("hot spots") have the highest affinity for the guest water molecules? (2) How stable are water clusters inside the cavity? (3) Which mode of water binding, sequential or bulk, is thermodynamically more favored? (4) What is the upper limit of the number of water molecules bound inside the host cavity? (5) What factors do control the CD hydration process? Here, using αCD as a typical representative of the cyclodextrin family, we endeavor to answer these questions by combining experimental measurements (differential scanning calorimetry and thermogravimetry) with theoretical (DFT) calculations. Enthalpies of the αCD hydrate formation are evaluated and the role of different factors, such as the number and mode of binding (sequential vs bulk) of water molecules, type of hydrogen bonds established (water-water vs water-αCD), and the dielectric properties of the medium, on the complexation process is assessed. The results obtained shed light on the intimate mechanism of water binding to αCD and disclose the key factors governing the process.

Microstructural investigations of carbon foams derived from modified coal-tar pitch.

This work reports the microstructural evaluation of carbon foams derived from coal-tar pitch precursors treated with H2SO4 and HNO3 and finally annealed at 1000°C and 2000°C. Our experimental investigations combine scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) imaging, X-ray photoelectron spectroscopy (XPS) and micro-spot near-edge X-ray absorption fine structure (µ-NEXAFS) spectroscopy. This set of complementary techniques provides detailed structural and chemical information of the surface and the bulk of the carbon foams. The high-resolution microscopy data indicate the formation of carbonaceous amorphous microspheres (average diameters of 0.28±0.01µm) embedded in the partially graphitized carbon foam matrix at 1000°C. The microspheres are enriched with sp-bonded species and their microstructural characteristics depend on the reagent (nitric vs. sulfuric acid) used for pitch treatment. A complete chemical transformation of the microspheres at temperatures >1000°C occurs and at 2000°C they are spectroscopically identical with the bulk material (sp(2)- and sp(3)-hybridised forms of carbon). The microstructure-property relationship is exemplified by the compressive strength measurements. These results allow a better description of coal-tar pitch-derived carbon foams at the atomic level, and may account for a better understanding of the processes during graphitization step.

Cyclodextrin-Based Solid-Gas Clathrates.

"Cyclodextrin-gas" clathrates were obtained by crystallization from water solution of α-, ß-, and γ-cyclodextrins (CDs) under pressure of the gas to be entrapped into the CD molecules. When the pressure is released, these clathrates are stable at ambient conditions and dissociate at elevated temperature, which makes them interesting for various applications as foam boosters in food and other industries. It was found that under these conditions α-CD forms clathrates with all of the gases used in this study (N2, N2O, CO2, Ar), whereas ß- and γ-CDs can form clathrates only with N2. The concentration of the cyclodextrin and the temperature and pressure of the gas were varied for achieving higher clathrate yield and larger amount of embedded gas. Highest values of about 2 wt % were found for α-CD-N2O, as it releases in the temperature range of 40-60 °C.