Introducing Spiro-locks into the Nitrogen/Carbonyl System towards Efficient Narrowband Deep-blue Multi-resonance TADF Emitters

The current availability of multi-resonance thermally activated delayed fluorescence (MR-TADF) materials with excellent color purity and high device efficiency in the deep-blue region is appealing. To address this issue in the emerged nitrogen/carbonyl MR-TADF system, we propose a spiro-lock strategy. By incorporating spiro functionalization into a concise molecular skeleton, a series of emitters (SFQ, SOQ, SSQ, and SSeQ) can enhance molecular rigidity, blue-shift the emission peak, narrow the emission band, increase the photoluminescence quantum yield by over 92 %, and suppress intermolecular interactions in the film state. The referent CZQ without spiro structure has a more planar skeleton, and its bluer emission in the solution state redshifts over 40 nm with serious spectrum broadening and a low PLQY in the film state. As a result, SSQ achieves an external quantum efficiency of 25.5 % with a peak at 456 nm and a small full width at half maximum of 31 nm in a simple unsensitized device, significantly outperforming CZQ. This work discloses the importance of spiro-junction in modulating deep-blue MR-TADF emitters.     

Polymerized Thermally Activated Delayed-Fluorescence Small Molecules: Long-Axis Polymerization Leads to a Nearly Concentration-Independent Luminescence

Nowadays numerous thermally activated delayed fluorescence (TADF) polymers have been developed for PLEDs to realize high device performance and tunable emission colors. However, they often possess a strong concentration dependence on their luminescence including aggregation-caused quenching (ACQ) and aggregation-induced emission (AIE). Herein, we first report a nearly concentration-independent TADF polymer based on the strategy of polymerized TADF small molecules. It is found that when a donor-acceptor-donor (D-A-D) type TADF small molecule is polymerized through its long-axis direction, the triplet state is distributed along the polymeric backbone to effectively suppress the unwanted concentration quenching. Unlike the short-axis one with an ACQ effect, the photoluminescent quantum yield (PLQY) of the resultant long-axis polymer remains almost unchanged with the increasing doping concentration. Accordingly, a promising external quantum efficiency (EQE) up to 20 % is successfully achieved in a whole doping control window of 5–100 wt. %.     

Solution-Processable Pure-Red Multiple Resonance-induced Thermally Activated Delayed Fluorescence Emitter for Organic Light-Emitting Diode with External Quantum Efficiency over 20 %

Developing solution-processable red organic light-emitting diodes (OLEDs) with high color purity and efficiency based on multiple resonance thermally activated delayed fluorescence (MR-TADF) is a formidable challenge. Herein, by introducing auxiliary electron donor and acceptor moieties into the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) distributed positions of multiple resonance skeleton simultaneously, an effective strategy to obtain red MR-TADF emitters was represented. The proof-of-the-concept molecule BN-R exhibits a narrowband pure-red emission at 624 nm, with a high luminous efficiency of 94 % and a narrow bandwidth of 46 nm. Notably, the fabricated solution-processable pure-red OLED based on BN-R exhibits a state-of-the-art external quantum efficiency over 20 % with the Commission Internationale de I’Éclairage coordinates of (0.663, 0.337) and a long operational lifetime (LT₅₀) of 1088 hours at an initial luminance of 1000 cd m⁻².     

Self-catalytic cross-linking reaction and reactive mechanism studies of α-aminomethyl triethoxysilanes for α,ω-dihydroxy poly(dimethylsiloxane)

Some kinds of aminomethyl triethoxysilanes, cross-linkers of α,ω-dihydroxy poly(dimethylsiloxane) (PDMS), can act as catalyst to self-catalyze the cross-linking reaction with PDMS, as found in our studies. Three kinds of α-aminomethylsilanes, [(diethyl)aminomethyl triethoxysilane (DMTS), anilinomethyl triethoxysilane (AMTS) and cyclohexylaminomethyl triethoxysilane (CMTS)], and two kinds of γ-aminopropyl silanes, [(γ-aminopropyl triethoxysilane (APTS) and (N-β-aminoethyl)-γ-aminopropyl triethoxysilane (AATS)] were selected to study the self-catalytic cross-linking reaction and its mechanism. The reactivity of the cross-linkers determined by n-hexane extraction experiments, was found to be DMTS > CMTS ? AMTS, but APTS and AATS could not react with PDMS without catalysis. The cross-linking degree was increased with the reactivity. The results of extraction experiments and Fourier transform infra-red (FT-IR) spectra indicated that the cross-linking reaction was an equimolar reaction between the Si-OH groups and Si-OC₂H₅ groups. Formation of electron conjugation of N and Si in α-aminomethyl triethoxysilane molecules has been proposed to elucidate the mechanism of the self-catalytic cross-linking reaction. The Modulated Differential Scanning Calorimeter (MDSC) results showed that the increase of the glass-transition temperature (T_g) of the cross-linked products was dependent on the reactivity of the cross-linkers. The thermo-gravimetric analysis (TGA) results demonstrated that the thermal stabilities of the cross-linked products were also related to the reactivity and the structures of the cross-linkers.     

基于水杨醛席夫碱锌配合物交联稳定化荧光聚合物胶束的合成及其对铜离子的荧光响应性

以S-十二烷基-S'-(α,α'-二甲基-α″-乙酸)-三硫代碳酸酯(DMAT)为链转移剂、2-羟基-5-乙烯基苯甲醛(HVB)为单体,利用可逆加成-断裂链转移自由基聚合法(RAFT)合成结构明确、数均相对分子质量可控的水杨醛聚合物(PHVB)。将PHVB直接地与单端胺基功能化聚乙二醇(m PEG-NH2)按n(—NH2group)/n(—CHO group)=0.50投料进行醛-胺缩合反应,获得接枝率为50%的两亲性接枝水杨醛席夫碱聚合物PHVB-graft-PEG。采用凝胶渗透色谱仪(GPC)和核磁共振氢谱(1H NMR)对合成的聚合物的数均相对分子质量和结构进行了确证。将PHVB-graft-PEG直接地分散于无水乙醇中,自组装形成以聚乙烯水杨醛席夫碱为核、聚乙二醇为壳的胶束,然后以所得胶束为微反应器,与Zn(OAc)2进行配位反应得到外壳为可溶性链段PEG,内核为发光水杨醛席夫碱锌配合物的PHVB-graft-PEG/Zn~(2+)交联稳定化胶束。通过紫外-可见分光光谱(UV-Vis)、荧光发射光谱(FLL)、动态光散射(DLS)和透射电子显微镜(TEM)分别对胶束的交联稳定化过程进行了表征。研究结果表明,经交联稳定化后,PHVB-graft-PEG/Zn~(2+)胶束在干燥后仍可在水和常见有机溶剂中再分散形成粒径大小约为100 nm、在约460 nm处发射出蓝光荧光的纳米粒子,并且可作为荧光传感器,在水溶液中对Cu~(2+)离子进行选择性识别,其荧光淬灭率与Cu~(2+)离子浓度(0~50μmol/L范围内)呈线性关系,最低检测下限至0.5μmol/L,而其它共存离子如Cd~(2+)、Mg~(2+)、Ni~(2+)、Pb~(2+)、Ca~(2+)、Hg~(2+)、Al3+、Mn~(2+)等对Cu~(2+)离子的荧光响应性没有干扰,即可实现对Cu~(2+)离子进行定量检测。     

Consensus seeking in multi-agent systems via hybrid protocols with impulse delays

This paper studies the consensus problem of multi-agent systems with both fixed and switching topologies. A hybrid consensus protocol is proposed to take into consideration of continuous-time communications among agents and delayed instant information exchanges on a sequence of discrete times. Based on the proposed algorithms, the multi-agent systems with the hybrid consensus protocols are described in the form of impulsive systems or impulsive switching systems. By employing results from matrix theory and algebraic graph theory, some sufficient conditions for the consensus of multi-agent systems with fixed and switching topologies are established, respectively. Our results show that, for small impulse delays, the hybrid consensus protocols can solve the consensus problem if the union of continuous-time and impulsive-time interaction digraphs contains a spanning tree frequently enough. Simulations are provided to demonstrate the effectiveness of the proposed consensus protocols.     

On the expected discounted penalty function for the compound Poisson risk model with delayed claims

In this paper, we consider an extension to the compound Poisson risk model for which the occurrence of the claim may be delayed. Two kinds of dependent claims, main claims and by-claims, are defined, where every by-claim is induced by the main claim and may be delayed with a certain probability. Both the expected discounted penalty functions with zero initial surplus and the Laplace transforms of the expected discounted penalty functions are obtained from an integro-differential equations system. We prove that the expected discounted penalty function satisfies a defective renewal equation. An exact representation for the solution of this equation is derived through an associated compound geometric distribution, and an analytic expression for this quantity is given for when the claim amounts from both classes are exponentially distributed. Moreover, the closed form expressions for the ruin probability and the distribution function of the surplus before ruin are obtained. We prove that the ruin probability for this risk model decreases as the probability of the delay of by-claims increases. Finally, numerical results are also provided to illustrate the applicability of our main result and the impact of the delay of by-claims on the expected discounted penalty functions.     

Quantification of myocardial viability distribution with Gd(DTPA) bolus-enhanced, signal intensity-based percent infarct mapping

Introduction

A substantial, common shortcoming of the currently used semiautomated techniques for the quantification of myocardial infarct with delayed enhancement magnetic resonance imaging is the assumption that the whole myocardial slab that corresponds to the hyperenhanced tomographic area is 100% nonviable. This assumption is, however, incorrect. To resolve this conflict, we have recently proposed the signal intensity percent-infarct mapping method and validated it in an ex vivo, canine experiment. The purpose of the current study has been the validation of the signal intensity percent-infarct mapping method in vivo, using a porcine model of reperfused myocardial infarct.

Methods

In swines (n=6), reperfused myocardial infarct was generated occluding for 90 min by an angioplasty balloon either the left anterior descending or the left circumflex coronary artery. To obtain DE images, Gd(DTPA) enhanced inversion-recovery fast gradient-echo acquisitions were carried out on day 28 after myocardial infarction. Scanning started 15 min after intravenous injection of 0.2 mmol/kg Gd(DTPA). At the end of the MRI session, the animal was sacrificed and 2,3,5-triphenyltetrazolium chloride staining was used to validate the existence and to determine the accurate size of the myocardial infarct. Tissue samples were taken and stained with hematoxylin-eosin and Masson's trichrome for histological assessment of the infarct and the periinfarct zone. The signal intensity percent-infarct mapping data were compared with corresponding data from the delayed enhancement images analyzed with SI_remote+2S.D. thresholding, and with corresponding triphenyltetrazolium-chloride staining data using Friedman's repeated measure analysis of variance on ranks.

Results

The infarct volume determined by the triphenyltetrazolium chloride, SI_remote+2S.D. and signal intensity percent-infarct mapping methods was 3.04 ml [2.74, 3.45], 13.62 ml [9.06, 18.45] and 4.27 ml [3.45, 6.33], respectively. Median infarct volume determined by SI_remote+2S.D. significantly differed from that determined by triphenyltetrazolium chloride (P<.05). The Bland-Altman overall bias was 12.49% of the volume of the left ventricle. Median infarct volume determined by signal intensity percent-infarct mapping, however, did not differ significantly (NS) from that obtained by triphenyltetrazolium chloride. Signal intensity percent-infarct mapping yielded only a 1.99% Bland-Altman overall bias of the left ventricular volume.

Conclusions

This in vivo study in the porcine reperfused myocardial infarct model demonstrates that signal intensity percent-infarct mapping is a highly accurate method for the determination of the extent of myocardial infarct. MRI images for signal intensity percent-infarct mapping are obtained with the pulse sequence of conventional delayed enhancement imaging and are acquired within clinically acceptable scanning time. This makes signal intensity percent-infarct mapping a practical method for clinical implementation.     

Nonlinear stability of traveling wave fronts for delayed reaction diffusion systems

This paper is concerned with nonlinear stability of traveling wave fronts for a delayed reaction diffusion system. We prove that the traveling wave front is exponentially stable to perturbation in some exponentially weighted L^∞ spaces, when the difference between initial data and traveling wave front decays exponentially as x→−∞, but the initial data can be suitable large in other locations. Moreover, the time decay rates are obtained by weighted energy estimates.