Restriction of Intramolecular Motion(RIM): Investigating AIE Mechanism from Experimental and Theoretical Studies

Mechanistic studies promote scientific development from phenomena to theories.Aggregation-induced emission(AIE),as an unusual photophysical phenomenon,builds the bridge between molecular science and aggregate mesoscience.With the twenty-year development of AIE,restriction of intramolecular motion(RIM)has been verified as the working mechanism of AIE effect.In this review,these mechanistic works about RIM are summarized from experimental and theoretical perspectives.Thereinto,the experimental studies are introduced from three parts:external rigidification,structural modification and structural characterization.In the theoretical part,calculations on the low-frequency motion of AIEgens have been performed to prove the RIM mechanism.By virtue of the theoretical calculations,some new mechanisms are proposed to supplement the RIM,such as restriction of access to conical intersection,suppression of Kasha transition,restriction of access to dark state,etc.It is foreseeable that the RIM mechanism will unify the photophysical theories for both molecules and aggregates,and inspire more progress in aggregate science.     

Water-in-Oil-in-Water Nanoemulsions Containing Temulawak (Curcuma xanthorriza Roxb) and Red Dragon Fruit (Hylocereus polyrhizus) Extracts

Hydrophobic curcumin in temulawak extract and hydrophilic betacyanin in red dragon fruit extract are high-value bioactive compounds with extensive applications in functional food. In this study, these extracts were encapsulated in water-in-oil-in-water (w/o/w) nanoemulsions as a delivery system using a two-step high-energy emulsification method. PGPR and Span 20 were used as lipophilic emulsifiers for the primary w/o emulsion. The most stable w/o/w formulation with the least oil phase separation of 5% v/v consisted of w/o emulsion (15% w/w) and Tween 80 (1.5% w/w) as hydrophilic emulsifier. The formulation was characterized by a 189-nm mean droplet diameter, 0.16 polydispersity index, and –32 mV zeta potential. The freeze–thaw stability may be attributed to the combination of low w/o emulsion content and high Tween 80 concentration in the outer water phase of the w/o/w nanoemulsions used in this study. The IC₅₀ values of the nanoemulsion and the red dragon fruit extract were similar. It means that the higher concentration of curcumin in the nanoemulsions and the lower IC₅₀ value of temulawak extract ensured sufficient antioxidant activities of the w/o/w nanoemulsions.     

Upgrading Solid Digestate from Anaerobic Digestion of Agricultural Waste as Performance Enhancer for Starch-Based Mulching Biofilm

Developing a green and sustainable method to upgrade biogas wastes into high value-added products is attracting more and more public attention. The application of solid residues as a performance enhancer in the manufacture of biofilms is a prospective way to replace conventional plastic based on fossil fuel. In this work, solid digestates from the anaerobic digestion of agricultural wastes, such as straw, cattle and chicken manures, were pretreated by an ultrasonic thermo-alkaline treatment to remove the nonfunctional compositions and then incorporated in plasticized starch paste to prepare mulching biofilms by the solution casting method. The results indicated that solid digestate particles dispersed homogenously in the starch matrix and gradually aggregated under the action of a hydrogen bond, leading to a transformation of the composites to a high crystalline structure. Consequently, the composite biofilm showed a higher tensile strength, elastic modulus, glass transition temperature and degradation temperature compared to the pure starch-based film. The light, water and GHG (greenhouse gas) barrier properties of the biofilm were also reinforced by the addition of solid digestates, performing well in sustaining the soil quality and minimizing N₂O or CH₄ emissions. As such, recycling solid digestates into a biodegradable plastic substitute not only creates a new business opportunity by producing high-performance biofilms but also reduces the environmental risk caused by biogas waste and plastics pollution.     

Computational Study of the Electron Spectra of Vapor-Phase Indole and Four Azaindoles

After geometry optimization, the electron spectra of indole and four azaindoles are calculated by density functional theory. Available experimental photoemission and excitation data for indole and 7-azaindole are used to compare with the theoretical values. The results for the other azaindoles are presented as predictions to help the interpretation of experimental spectra when they become available.     

NiFe2O4对刚果红的光催化降解性能研究

采用水热法合成了尖晶石型NiFe₂O₄,并利用X射线粉末衍射仪对其物相进行了表征,利用紫外-可见分光光度计对其光催化降解刚果红的性能进行了研究。以刚果红为光催化降解底物,探究了刚果红初始浓度、催化剂用量、溶液pH、不同光源等因素对NiFe₂O₄光催化降解刚果红活性的影响。结果表明,当刚果红溶液浓度为20 mg/L、催化剂NiFe₂O₄的用量为0.065 g、pH 2~10、在太阳光下照射480 min时,刚果红的降解率高达99%以上,催化剂性能稳定,适合处理刚果红类有机污染物。     

用于宽谱带发射白色发光二极管的黄色荧光粉Sr8MgAl(PO4)7∶xEu2+的制备及发光性能

通过高温固相反应合成了一系列宽谱带发射黄色荧光粉Sr_8MgAl(PO_4)_7∶x Eu~(2+)(SMAP∶x Eu~(2+)),并对其物质结构、发光性能及其在白色发光二极管(WLED)领域的应用进行了探究。X射线衍射(XRD)测试结果表明,SMAP∶x Eu~(2+)系列荧光粉具有单斜结构和C2/m空间群,激活剂Eu~(2+)离子能够很好地进入SMAP基质中并占据Sr~(2+)离子的晶格位点。漫反射光谱分析显示SMAP基质属于宽带隙材料,带隙宽度为3.60 e V。此外,SMAP∶x Eu~(2+)具有较宽的激发范围(280～500 nm),对应于Eu~(2+)离子的4f~7→4f~65d~1跃迁;在380 nm近紫外光激发下,呈现出450～800 nm的多发光中心的非对称黄光发射,发射峰位于590 nm处。基于高斯多峰拟合结果,得到3个发光中心,分别位于528、600和680 nm。最后,将已制备的黄色荧光粉SMAP∶0.05Eu~(2+)与商业化蓝粉Ba Mg Al_(10)O_(17)∶Eu~(2+)混合涂覆到400 nm芯片上制得色温较好(3 344 K)、显色指数较高(90.1)的WLED。     

Interface Amorphization of Two-Dimensional Black Phosphorus upon Treatment with Diazonium Salts

Two-dimensional (2D) black phosphorus (BP) represents one of the most appealing 2D materials due to its electronic, optical, and chemical properties. Many strategies have been pursued to face its environmental instability, covalent functionalization being one of the most promising. However, the extremely low functionalization degrees and the limitations in proving the nature of the covalent functionalization still represent challenges in many of these sheet architectures reported to date. Here we shine light on the structural evolution of 2D-BP upon the addition of electrophilic diazonium salts. We demonstrated the absence of covalent functionalization in both the neutral and the reductive routes, observing in the latter case an unexpected interface conversion of BP to red phosphorus (RP), as characterized by Raman, ³¹P-MAS NMR, and X-ray photoelectron spectroscopies (XPS). Furthermore, thermogravimetric analysis coupled to gas chromatography and mass spectrometry (TG-GC-MS), as well as electron paramagnetic resonance (EPR) gave insights into the potential underlying radical mechanism, suggesting a Sandmeyer-like reaction.     

An Iridium Complex as an AIE-active Photosensitizer for Image-guided Photodynamic Therapy

Image-guided photodynamic therapy (PDT) has received growing attention due to its non-invasiveness and precise controllability. However, the PDT efficiency of most photosensitizers are decreased in living system due to the aggregation-caused singlet oxygen (¹O₂) generation decreasing. Herein, we present an Iridium (III) pyridylpyrrole complex (Ir-1) featuring of aggregation-induced emission (AIE) and ¹O₂ generation characteristics for image-guided PDT of cancer. Ir-1 aqueous solution exhibits bright red phosphorescence peaked at 630 nm, large Stokes shift of 227 nm, and good ¹O₂ generation ability. The ¹O₂ generating rate of Ir-1 in EtOH/water mixture solution is 2.3 times higher than that of Rose Bengal. In vitro experimental results revealed that Ir-1 has better biocompatibility and higher phototoxicity compared with clinically used photosensitizers (Rose Bengal and Ce6), suggesting that Ir-1 can serve as a photosensitizer for image-guided PDT of cancer.     

Controlling Energy Gaps of π-Conjugated Polymers by Multi-Fluorinated Boron-Fused Azobenzene Acceptors for Highly Efficient Near-Infrared Emission

We demonstrate that multi-fluorinated boron-fused azobenzene (BAz) complexes can work as a strong electron acceptor in electron donor-acceptor (D-A) type π-conjugated polymers. Position-dependent substitution effects were revealed, and the energy level of the lowest unoccupied molecular orbital (LUMO) was critically decreased by fluorination. As a result, the obtained polymers showed near-infrared (NIR) emission (λ_PL=758–847 nm) with high absolute photoluminescence quantum yield (Φ_PL=7–23%) originating from low-lying LUMO energy levels of the BAz moieties (−3.94 to −4.25 eV). Owing to inherent solid-state emissive properties of the BAz units, deeper NIR emission (λ_PL=852980 nm) was detected in film state. Clear solvent effects prove that the NIR emission is from a charge transfer state originating from a strong D-A interaction. The effects of fluorination on the frontier orbitals are well understandable and predictable by theoretical calculation with density functional theory. This study demonstrates the effectiveness of fluorination to the BAz units for producing a strong electron-accepting unit through fine-tuning of energy gaps, which can be the promising strategy for designing NIR absorptive and emissive materials.     

Twisted Phenanthro[9,10-d]imidazole Derivatives as Non-doped Emitters for Efficient Electroluminescent Devices with Ultra-Deep Blue Emission and High Exciton Utilization Efficiency

Herein, two deep-blue emissive molecules ( SAF-PI and SAF-DPI ) are designed and synthesized using spiro[acridine-9,9’-fluorene] as a donor (D) substituted with 2-(3-methylphenyl)-1-phenyl-phenanthro[9,10-d]imidazole as an acceptor (A), forming twisted D−A and A−D−A structures, respectively. The photophysical studies and density functional theory (DFT) calculations reveal that both molecules exhibit hybridized local excited and charge transfer (HLCT) characteristics with deep blue emission color. They are effectively applied as non-doped emitters in OLEDs. Particularly, SAF-PI -based device achieves the high-definition television (HDTV) standard blue color emission peaked at 428 nm with CIE coordinate of (0.156, 0.053), a narrow full width at half maximum of 55 nm, a maximum external quantum efficiency (EQE_max) of 4.57% and an exciton utilization efficiency of 65%.