High-Performance Solution-Processed Nondoped Circularly Polarized OLEDs with Chiral Triptycene Scaffold-Based TADF Emitters Realizing Over 20% External Quantum Efficiency

Recently, circularly polarized organic light-emitting diodes (CP-OLEDs) fabricated with thermally activated delayed fluorescence (TADF) emitters are developed rapidly. However, most devices are fabricated by vacuum deposition technology, and developing efficient solution-processed CP-OLEDs, especially nondoped devices, is still a challenge. Herein, a pair of triptycene-based enantiomers, (S,S)-/(R,R)-TpAc-TRZ, are synthesized. The novel chiral triptycene scaffold of enantiomers avoids their intermolecular π–π stacking, which is conducive to their aggregation-induced emission characteristics and high photoluminescence quantum yield of 85% in the solid state. Moreover, the triptycene-based enantiomers exhibit efficient TADF activities with a small singlet-triplet energy gap (ΔE_ST) of 0.03 eV and delayed fluorescence lifetime of 1.1 µs, as well as intense circularly polarized luminescence with dissymmetry factors (|g_PL|) of about 1.9 × 10⁻³. The solution-processed nondoped CP-OLEDs based on (S,S)-/(R,R)-TpAc-TRZ not only display obvious circularly polarized electroluminescence signals with g_EL values of +1.5 × 10⁻³ and −2.0 × 10⁻³, respectively, but also achieve high efficiencies with external quantum, current, and power efficiency up to 25.5%, 88.6 cd A⁻¹, and 95.9 lm W⁻¹, respectively.     

Maskless Preparation of Spatially-Resolved Plasmonic Nanoparticles on Polydimethylsiloxane via In Situ Fluoride-Assisted Synthesis

Here, a fluoride-assisted route for the controlled in-situ synthesis of metal nanoparticles (NPs) (i.e., AgNPs, AuNPs) on polydimethylsiloxane (PDMS) is reported. The size and coverage of the NPs on the PDMS surface are modulated with time and over space during the synthetic process, leveraging the improved yield (10×) and faster kinetics (100×) of NP formation in the presence of F⁻ ions, compared to fluoride-free approaches. This enables the maskless preparation of both linear and step gradients and patterns of NPs in 1D and 2D on the PDMS surface. As an application in flexible plasmonics/photonics, continuous and step-wise spatial modulations of the plasmonic features of PDMS slabs with 1D and 2D AgNP gradients on the surface are demonstrated. An excellent spatially resolved tuning of key optical parameters, namely, optical density from zero to 5 and extinction ratio up to 100 dB, is achieved with AgNP gradients prepared in AgF solution for 12 minutes; the performance are comparable to those of commercial dielectric/interference filters. When used as a rejection filter in optical fluorescence microscopy, the AgNP-PDMS slabs are able to reject the excitation laser at 405 nm and retain the green fluorescence of microbeads (100 µm) used as test cases.     

Diporphyrin tweezer for multichannel spectroscopic analysis of enantiomeric excess

Chiral 1,1’-binaphthyl-linked diporphyrin ‘tweezers’ (R)-1/(S)-1 and the corresponding zinc(II) complexes (R)-2/(S)-2 were prepared as chiral host molecules, and their utility for chiral analyses (especially enantiomeric excess (ee) determinations) were evaluated. Tris(1-n-dodecyl)porphyrins were used for the first time as the interacting units. Host capabilities of the diporphyrin tweezers were investigated by titrations with (R,R)- and (S,S)-cyclohexane-1,2-diamine (CHDA). The host molecules could be used as multichannel probes of ee by using UV-vis, circular dichroism (CD), fluorescence emission and ¹H nuclear magnetic resonance (¹H-NMR) methods. Chiral configurations could also be differentiated using CD or ¹H-NMR spectroscopy. All three optical techniques give good resolution of ee with reasonable sensitivity considering the low concentrations used (ca. 10⁻⁶ mol·L⁻¹). The ee determination of CHDA enantiomers using NMR spectroscopy is also possible because of the reasonably well separated resonances in the case of (R,R)- and (S,S)-CHDA. Non-metallated (R)-1/(S)-1 hosts could not be used to detect chiral information in a strongly acidic chiral guest. This work demonstrates the utility of 1,1’-binapthyl-linked chiral hosts for chiral analysis of ditopically interacting enantiomers.     

Detecting Cysteine in Bioimaging with a Near-Infrared Probe Based on a Novel Fluorescence Quenching Mechanism

Near-infrared (NIR) fluorescent probes are very significant for detecting cysteine in biological systems. Herein, we report a highly selective and sensitive NIR turn-on fluorescent probe (BDP-NIR) based on BODIPY with large Stokes shift (105 nm) for detecting Cys. We clarified the sensing mechanism based on the different thiol-induced S_NAr substitution/rearrangement reaction of the probe with cysteine and homocysteine/glutathione, which leads to the corresponding amino- and thiol-BODIPY dyes with distinct photophysical properties. Moreover, a novel mechanism of fluorescence quenching was demonstrated by density functional theory calculation. The reason for the fluorescence quenching of the probe might be intersystem crossing (from singlet to triplet excited state). Moreover, BDP-NIR had a high linear dynamic range of 0–500 μM, which was promising for detecting cysteine quantificationally. Significantly, BDP-NIR was capable of sensing endogenous cysteine in living cells and in vivo.     

Preparation of molecularly imprinted fluorescence sensor based on carbon quantum dots via precipitation polymerization for fluorescence detection of tetracycline

A facile and effective method was proposed to prepare the molecularly imprinted fluorescence sensor with carbon quantum dots, which were modified vinyl groups by acrylic acid on the surface. The obtained fluorescence composite material was investigated by transmission electron microscope and Fourier transform infrared spectra. After the experimental conditions were optimized, a linear range of 1.0–60 μmol L⁻¹ was obtained and the detection limit was 0.17 μmol L⁻¹. The novel fluorescence sensor can be successfully used to detect tetracycline in real samples. This study provides a convenient strategy for selective recognition and rapid detection of tetracycline in the complex environment.     

不同有机物对硝酸盐氮测试的影响

研究了红糖、葡萄糖、乙酸钠、甲醇、乙醇、乙酸、丙酸、丁酸、正戊酸、混合有机溶剂等10种不同有机物对麝香草酚光谱法和离子色谱法测试硝酸盐氮的影响。结果表明,溶液中含有红糖或葡萄糖时,均会对麝香草酚法测试硝酸盐氮造成影响,使得测试结果偏大;在无硝酸根离子存在时,红糖和葡萄糖的质量浓度与硝酸盐氮的测试浓度非线性相关;而乙酸钠、甲醇、乙醇、乙酸、丙酸、丁酸、正戊酸和混合有机溶剂则对麝香草酚法测试硝酸盐氮没有影响。实验发现,红糖和葡萄糖在浓硫酸的作用下与麝香草酚发生Molisch反应,形成有色复合物和红棕色不溶性沉淀。实验采用离子色谱法测试硝酸盐氮时,红糖和葡萄糖等糖类有机物对测试结果均无影响。     

氢化物原子荧光光谱法测定酱油中微量铅的方法研究

建立了一种快速、高效的QuEChERS-高效液相色谱-质谱联用法（QuEChERS-HPLC-MS/MS）测定谷类杂粮制品中脱氧雪腐镰刀菌烯醇（DON）、3-乙酰脱氧雪腐镰刀菌烯醇（3-ADON）、15-乙酰脱氧雪腐镰刀菌烯醇（15-ADON）和玉米赤霉烯酮（ZON）共4种真菌毒素。样品前处理采用乙腈-水溶剂提取，经Florisil+C18+无水硫酸镁净化后检测。以0.10%甲酸-乙腈作为流动相，在质谱检测器的多反应监测模式下进行分析。结果表明，4种真菌毒素在各自的线性范围内线性关系良好，相关系数R2均大于0.999，回收率在85.1%～102.0%，相对标准偏差（RSD）为2.11%～6.22%。该方法具有前处理简单、净化效果好、灵敏度高和检测速度快的优点，适用于谷类杂粮制品中DON、3-ADON、15-ADON 和ZON的分析和定量检测。