Facile Generation of Thermally Activated Delayed Fluorescence and Fabrication of Highly Efficient Non-Doped OLEDs Based on Triazine Derivatives

A series of donor–acceptor–donor triazine-based molecules with thermally activated delayed fluorescence (TADF) properties were synthesized to obtain highly efficient blue-emitting OLEDs with non-doped emitting layers (EMLs). The targeted molecules use a triazine core as the electron acceptor, and a benzene ring as the conjugated linker with different electron donors to alternate the energy level of the HOMO to further tune the emission color. The introduction of long alkyl chains on the triazine core inhibits the unwanted intermolecular D –D/A–A-type π–π interactions, resulting in the intermolecular D–A charge transfer. The weak aggregation-caused quenching (ACQ) effect caused by the suppressed intermolecular D –D/A–A-type π–π interaction further enhances the emission. The crowded molecular structure allows the electron donor and acceptor to be nearly orthogonal, thereby reducing the energy gap between triplet and singlet excited states (ΔE_ST). As a result, blue-emitting devices with TH-2DMAC and TH-2DPAC non-doped EMLs showed satisfactory efficiencies of 12.8 % and 15.8 %, respectively, which is one of the highest external quantum efficiency (EQEs) reported for blue TADF emitters (λ_peak<475 nm), demonstrating that our tailored molecular designs are promising strategies to endow OLEDs with excellent electroluminescent performances.     

Tunable wetting mechanism of polypyrrole surfaces and low-voltage droplet manipulation via redox

This paper presents the experimental results and analyses on a controlled manipulation of liquid droplets upon local reduction and oxidation (redox) of a smart polymer-dodecylbenzenesulfonate doped polypyrrole (PPy(DBS)). The electrochemically tunable wetting property of PPy(DBS) permitted liquid droplet manipulation at very low voltages (-0.9 to 0.6 V). A dichloromethane (DCM) droplet was flattened upon PPy(DBS) reduction. It was found that the surface tension gradient across the droplet contact line induced Marangoni stress, which caused this deformation. Further observation of PPy(DBS)'s color change upon the redox process confirmed that the surface tension gradient was the driving force for the droplet shape change.     

Engineered Bifunctional Luminescent Pillared-Layer Frameworks for Adsorption of CO2 and Sensitive Detection of Nitrobenzene in Aqueous Media

Through a dual-ligand synthetic approach, five isoreticular primitive cubic (pcu)-type pillared-layer metal–organic frameworks (MOFs), [Zn₂(dicarboxylate)₂(NI-bpy-44)] ⋅ x DMF ⋅ y H₂O, in which dicarboxylate=1,4-bdc ( 1 ), Br-1,4-bdc ( 2 ), NH₂-1,4-bdc ( 3 ), 2,6-ndc ( 4 ), and bpdc ( 5 ), have been engineered. MOFs 1 – 5 feature twofold degrees of interpenetration and have open pores of 27.0, 33.6, 36.8, 52.5, and 62.1 %, respectively. Nitrogen adsorption isotherms of activated MOFs 1′ – 5′ at 77 K all displayed type I adsorption behavior, suggesting their microporous nature. Although 1′ and 3′ – 5′ exhibited type I adsorption isotherms of CO₂ at 195 K, MOF 2′ showed a two-step gate-opening sorption isotherm of CO₂. Furthermore, MOF 3′ also had a significant influence of amine functions on CO₂ uptake at high temperature due to the CO₂–framework interactions. MOFs 1 – 5 revealed solvent-dependent fluorescence properties; their strong blue-light emissions in aqueous suspensions were efficiently quenched by trace amounts of nitrobenzene (NB), with limits of detection of 4.54, 5.73, 1.88, 2.30, and 2.26 μm , respectively, and Stern–Volmer quenching constants (K_sv) of 2.93×10³, 1.79×10³, 3.78×10³, 4.04×10³, and 3.21×10³ m ⁻¹, respectively. Of particular note, the NB-included framework, NB@ 3 , provided direct evidence of the binding sites, which showed strong host–guest π–π and hydrogen-bonding interactions beneficial for donor–acceptor electron transfer and resulting in fluorescence quenching.     

Quantitative analysis of multiple urinary biomarkers of carcinoid tumors through gold-nanoparticle-assisted laser desorption/ionization time-of-flight mass spectrometry

A simple technique for quantitative analysis of four urinary biomarkers, tryptophan (TRP), 5-hydroxytryptophan (5-HTP), 5-hydroxytryptamine (5-HT) and 5-hydroxyindole acetic acid (5-HIAA) of carcinoid tumors is developed using gold nanoparticles as the assisted matrix in surface-assisted laser desorption/ionization time-of-flight mass spectrometry (SALDI–TOF MS). The optimal SALDI conditions for the efficient ionization of those biomarkers are systematically explored by the adjustments of the concentrations of gold nanoparticles and internal standards. The mass spectra with strong signals and minimal background noise are obtained using 1-naphthaleneacetamide (NAD) as the internal standard. The calibration curves of the biomarker concentrations are determined using SALDI–TOF MS and the high linearity is obtained in all samples. For future clinical testing, multiplexed detection of those biomarkers in the urine samples of healthy males is performed. The successful quantitative detections of TRP, 5-HTP, 5-HT and 5-HIAA indicate that our technique provided great potentials to be developed a simple and rapid platform for the tumor biomarker detections.     

Crystal packing effects within [Mn3O] single-molecule magnets: Controlling intermolecular antiferromagnetic interactions

The reactions of 2-hydroxyphenylethanone oxime (Me-H₂salox) and (2-hydroxy-phenyl)-phenyl-methanone oxime (Ph-H₂salox) with Mn(ClO₄)₂·6H₂O in MeOH afford trinuclear manganese complexes of [Mn₃O(Me-salox)₃(MeOH)₃(ClO₄)]·MeOH (1·MeOH) and [Mn₃O(Ph-salox)₃(MeOH)₃(ClO₄)]·2MeOH (2·2MeOH), respectively. X-ray analysis shows that both complexes contain a manganese triangle core, [Mn^III₃O]⁷⁺. The structural distortion from the twisting of the oxime ligands dominates the ferromagnetic interactions within the three Mn ions in both compounds and results in an S = 6 ground state. The frequency dependence of out-of-phase signals in the alternating current (AC) magnetic susceptibility measurements and the temperature-dependent and sweep-rate-dependent hysteresis loops are indicative of single-molecule magnet behavior. Moreover, both complexes show step-wise magnetization, indicating the occurrence of quantum tunneling of magnetization (QTM). Interestingly, a tail to tail arrangement in the crystal packing of complex 1·MeOH results in strong intermolecular H-bonding interactions and leads to the exchange-bias effect from the antiferromagnetic interaction between the adjacent Mn₃ molecules. In contract, QTM steps of complex 2·2MeOH show an absence of the exchange-bias effect due to a weak intermolecular interaction from a head to tail arrangement.     

Quantitative analysis of multiple urinary biomarkers of carcinoid tumors through gold-nanoparticle-assisted laser desorption/ionization time-of-flight mass spectrometry

A highly selective and sensitive coumarin-based chemodosimeter 1 for Cu(2+) in water is reported in this work. 1 was designed and facilely synthesized by a one-step reaction with coumarin as a fluorophore and 2-picolinic acid as the binding moiety, which showed very week fluorescence in buffer solution, and its fluorescence was considerably enhanced by the addition of Cu(2+) at room temperature in 5 min. Mechanism study suggested that Cu(2+) promoted the hydrolysis of 1 via the catalytic sensing cycle, generating a highly fluorescent product 7-hydroxycoumarin with fluorescence signal greatly amplified. The probe exhibited remarkably selective fluorescence enhancement to Cu(2+) over other metal ions at 454 nm, with a detection limit of 35 nM Cu(2+). Under optimal condition, 1 was successfully used for the determination of Cu(2+) in fetal equine serum and two water samples.     

Examination of vanadium contaminated pillared rectorite catalysts with the atomic force microscope

When vanadyl naphthanate solutions in toluene are used to V-contaminate rectorite pillared with alumina clusters, V migration from the pillared clay microporous structure to the outer surface occurs during the thermal treatments used in catalyst preparation. The presence of V on the clay catalyst surface can be inferred from atomic force microscopy (AFM) images showing a marked decrease in surface roughness resulting from the presence of vanadia. AFM images show what are believed to be islands as well as stacks of vanadia layers on the clay surface. Irrespective of the thermal and hydrothermal treatments used to prepare these catalysts, atomic scale details of V-contaminated clay samples retain the surface parameters characteristic of the silicate layers in smectites. These results suggest that V on the clay surface is present as V=O groups attached to the three basal oxygens of the SiO₄ units that form the clay silicate layers. These VO units form an hexagonal arrangement of white spots having next neighbor (d_c) and lateral distance (d_l) of 5.2 Å and 9.1 Å, respectively.     

MALDI-mass spectrometry imaging of desalted rat brain sections reveals ischemia-mediated changes of lipids

Ischemia-mediated lipidomic changes in rat brains were explored by matrix-assisted laser desorption/ionization-mass spectrometry (MALDI-MS) profiling and imaging after in situ desalting which drastically simplified the spectral presentation of tissue lipids. Removal of interference from the massively changed cations in response to tissue damage permitted the revelation of subtle yet important lipidomic changes. The identities of the detected lipids were confirmed by MALDI tandem mass spectrometry (MALDI-MS/MS). The MALDI-MS imaging (MALDI-MSI) result of lysophosphatidylcholine 16:0 (LPC 16:0) in the desalted brain section appeared essentially identical to that of sodiated LPC 16:0 in the adjacent undesalted section and verified the suitability of the desalting method for the MALDI-MSI studies of lipids in tissue. Other than the consistently decreased phosphatidylcholine (PC) 16:0/18:1, images of PCs containing all saturated, or combined saturated and monounsaturated fatty acyl (MUFA) residues revealed their parenchymal increase by ischemia. Images of PCs containing polyunsaturated fatty acyl (PUFA) residues in normal cortex showed laminated patterns similar to cortical lamina. Ischemia reduced the abundance of PC 16:0/20:4 and PC 16:0/22:6 and disrupted the laminated distribution of the former. However, ischemia increased the subcortical abundance of PUFA-PCs containing stearoyl residue and confined their cortical increase within limited areas. Image of parenchymal sphingomyelin 18:0 (SM 18:0) showed its consistent decrease by ischemia that paralleled the increase of ceramide 18:0-H(2)O in region of moderate to high SM abundance. The above results presented the lipidomic changes largely different from previous MALDI-MSI results and suggested a window of intervention that may benefit the management of cerebrovascular accident and other brain injuries.     

Environmental radiation detected at Lin Shin hospital in Taichung during the Fukushima nuclear power plant accident

This work is the first evaluation of environmental gamma exposure rates by the Nuclear Medicine Department at Lin Shin Hospital (LSH) in Taichung with Thermoluminescent dosimeter (TLD-100H) during the Fukushima Nuclear Power Plant (FNPP) accident. After the 9.0 M_W strong earthquake hit northern Japan on March 11, 2011, a TLD-100H was used to monitor environmental kerma rate at Taichung (2,500 km away from northern Japan) from Mar-08 to Apr-09, 2011 and evaluated kerma rate due to global fallout of the sever FNPP accidents. Exposure rates varied widely among positions close to the PET/CT facility. Observed kerma rates of up to 4.12 ± 0.62 mSv mo⁻¹ indicated an explicit, heavy leakage of photon through the PET/CT facility. No significant contributions were detected at Taichung, Taiwan. Hence, the health effect cause by the “extra radiation” from FNPP accidents is negligible. As this was a rare case of environmental monitoring during a nuclear power plant accident, its findings are of considerable significance.     

Nickel,copper and manganese hexacyanoferrate with poly(3,4-ethylenedioxythiophene) hybrid film modified electrode for selectively determination of ascorbic acid

The NiHCF-PEDOT, CuHCF-PEDOT and MnHCF-PEDOT films were prepared on glassy carbon electrode (GCE) by multiple scan cyclic voltammetry and characterized using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and scanning electron microscope (SEM) techniques. The advantages of these films are demonstrated for selectivity detection of ascorbic acid using cyclic voltammetry and amperometric method. Interestingly, the NiHCF-PEDOT and CuHCF-PEDOT modified electrodes exhibited a wide linear response range (5 × 10⁻⁶−3 × 10⁻⁴ M, R ² = 0.9973 and 1.8 × 10⁻³−1.8 × 10⁻² M, R ² = 0.9924). The electrochemical sensors facilitated the oxidation of AA but not responded to other electroactive biomolecules such as dopamine, uric acid, H₂O₂, glucose. The difference is MnHCF-PEDOT/GCE that no response to AA. In addition, the NiHCF-PEDOT and CuHCF-PEDOT modified electrodes exhibited a distinct advantage of simple preparation, specificity, stability and reproducibility.