Self-assembly of telechelic polymers bearing adamantane groups via host-guest inclusion complexes with cyclodextrin polymer

Self-assembly and supramolecular inclusion complexations between telechelic polymers bearing one or double adamantane groups and linear poly(β-cyclodextrin) (P(β-CD)) were investigated in water. An adamantane (Ada) attached to poly (acrylic acid) (PAA) was prepared by reversible addition-fragmentation chain transfer polymerization using s-1-dodecyl-s″ -(α,α′-dimethyl-α″-acetic acid) trithio-carbonate functionalized Ada with tert-butyl acrylate, followed by functional modification. Additionally, two Ada groups capped triblock copolymer F127 were obtained via an esterification reaction. The dynamic light scattering, transmission electron microscope and ¹H 2D NOSEY NMR spectroscopy were conducted to characterize the self-assembly behaviors. With the inclusion complexation of Ada/CD in 1:1 M ratio in water, the spherical micelles were enlarged at 25°C than that of the adamantyl polymer precursors. Due to the PPO segment of Ada-F127-Ada, the micelles aggregation showed temperature dependence from 4 to 37°C for precursor and corresponding inclusion complexation; while in Ada-PAA/P(β-CD) system, the hydrodynamic diameters decreased with pH decreasing.     

Synthesis of water dispersible reduced graphene oxide via supramolecular complexation with modified β-cyclodextrin

A noncovalent functionalization of the edges of reduced graphene oxide (RGO) with β-cyclodextrin-graft-hyperbranched polyglycerol (β-CD-g-HPG) was successfully performed via a host-guest interaction. The results showed that β-CD-g-HPG disperses the graphene sheets better than pure β-CD or HPG. The resulted supramolecular structure is stable in neutral water medium more than one week. However, in acidic medium the host-guest interaction is collapsed and graphene nanosheets precipitate.     

Efficient Host-Guest Complexation of a Bisporphyrin Host with Electron Deficient Guests: Synthesis,Structure, and Photoinduced Electron Transfer

The encapsulation of 1,8-naphthalic anhydride (NAN), 9-dicyanomethylenefluorene (9-DCF), acenaphthenequinone (ANQ), and 4-chloro-7-nitrobenzofurazan (NBD-Cl) by diethylpyrrole-bridged bisporphyrin (H₄DEP) and its dizinc(II) analogue (Zn₂DEP) are employed to investigate the structural and spectroscopic changes within the bisporphyrin cavity upon substrate binding. Synthesis and X-ray structures of all four encapsulated host-guest complexes (H₄DEP⋅NAN, H₄DEP⋅9-DCF, Zn₂DEP⋅ANQ, and Zn₂DEP⋅NBD-Cl) are reported here. The binding constant calculations show strong 1 : 1 binding between the hosts (H₄DEP and Zn₂DEP) and the guests (NAN/9-DCF/ANQ/NBD-Cl). ¹H-NMR spectra also support the retention of the host-guest assemblies in solution. Negative and positive shifts of the reduction and oxidation potentials, respectively, indicate that it is difficult to reduce/oxidize the encapsulated complexes. The emission intensities of the bisporphyrins (H₄DEP and Zn₂DEP) are substantially quenched in all the complexes, owing to photoinduced electron transfer from the excited state of the bisporphyrins to guest molecules. All the experimental evidence is further substantiated by DFT calculations. Such an efficient electron transfer is only possible when the donor and the acceptor moieties are in close propinquity to each other, which eventually lowers the reorganization energy.     

Organic Host Materials for Solution-Processed Phosphorescent Organic Light-Emitting Diodes

As a new technology for flat-panel displays and general lighting sources, solution-processed phosphorescent organic light-emitting diodes (PhOLEDs) unfurl a bright future, due to their merits of high quantum efficiency and easy fabrication. In recent years, great progress has been made in the device performance of solution-processed PhOLEDs, by developing both high-efficiency organometallic phosphors and novel solution-processable organic host materials. This review highlights recently developed organic host materials for triplet guest emitters in solution-processed PhOLEDs. The solution-processable host materials are classified into three types – small molecule, dendrimer, and polymer – according to their molecular architecture and molecular weight. The material design concept and the relationships between the molecular structure, material properties and device performance are the focus of this discussion. A future strategy for the development of high-performance solution-processed host materials is proposed.     

Hybrid Organic Light-Emitting Diodes with Low Color-Temperature and High Efficiency for Physiologically-Friendly Night Illumination

Low color-temperature (CT) light sources are preferred for physiologically-friendly illumination at night due to their low suppression of melatonin secretion. We fabricated low-CT hybrid organic light-emitting diodes (OLEDs) by constructing a double emissive-layer (EML) structure, with a blue-red fluorescent-phosphorescent hybrid EML and a green phosphorescent EML, separated by a bipolar interlayer. By doping a red phosphor in a blue fluorescent mixed-host with a decent concentration, blue and red emissions from the host and dopant, respectively, were obtained. The CT of the optimized device was tuned to less than 2500 K, with the brightness ranging from 100 to 10,000 cd m⁻². In addition, the low-CT OLED exhibited much higher efficacy than other low-CT light sources, such as incandescent bulbs and candles. The maximum power efficiency and external quantum efficiency of the hybrid OLED reached 54.6 lm W⁻¹ and 24.3 %, respectively, which only rolled off to 44.2 lm W⁻¹ and 23.6 % at 1000 cd m⁻², with a CT of 1910 K. Low-CT OLEDs with high efficacy provide a promising alternative for night lighting that will safeguard human health.     

Interrogating the Behaviour of a Styryl Dye Interacting with a Mesoscopic 2D-MOF and Its Luminescent Vapochromic Sensing

In this contribution, we report on the solid-state-photodynamical properties and further applications of a low dimensional composite material composed by the luminescent trans-4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran (DCM) dye interacting with a two-dimensional-metal organic framework (2D-MOF), Al-ITQ-HB. Three different samples with increasing concentration of DCM are synthesized and characterized. The broad UV-visible absorption spectra of the DCM/Al-ITQ-HB composites reflect the presence of different species of DCM molecules (monomers and aggregates). In contrast, the emission spectra are narrower and exhibit a bathochromic shift upon increasing the DCM concentration, in agreeance with the formation of adsorbed aggregates. Time-resolved picosecond (ps)-experiments reveal multi-exponential behaviors of the excited composites, further confirming the heterogeneous nature of the samples. Remarkably, DCM/Al-ITQ-HB fluorescence is sensitive to vapors of electron donor aromatic amine compounds like aniline, methylaniline, and benzylamine due to a H-bonding-induced electron transfer (ET) process from the analyte to the surface-adsorbed DCM. These findings bring new insights on the photobehavior of a well-known dye when interacting with a 2D-MOF and its possible application in sensing aniline derivatives.     

金属有机框架化合物在荧光识别方面的研究进展

通过荧光识别化合物是一种简单可靠、方便快捷的一种分析手段。金属有机框架(metalorganic frameworks, MOFs)通过框架和客体分子之间的相互作用,在荧光识别和传感等领域有着广阔的应用前景而成为一个热点研究领域。主要综述了金属有机框架在荧光识别溶剂小分子、离子、芳香有机分子以及气体分子等领域的研究工作。     

分子筛基纳米复合防晒剂的制备和表征及应用研究

利用离子交换法制备了一种新型的分子筛基主客体纳米复合FeO3-Y防晒剂。通过XRD、ICP、TEM和UV-vis等分析表征手段证实：由于客体团簇在分子筛的孔道中有序排列,即使在较低的含量下,这种主客体复合体系依然表现出很高的紫外吸收作用。与商品级纳米二氧化钛相比,这种防晒剂由于不具有光催化氧化性和透皮的安全隐患,所以具有更高的安全性。在粉底化妆品中的初步应用研究结果表明：这种复合防晒剂在配方中表现出了明显的抗紫外性质,与纳米二氧化钛复配后其抗紫外性质有很大提高。     

Inclusion Compounds of Dehydrocholic Acid with Solvents

The host-guest inclusion of various organic solvents within dehydrocholic acid has been studied and the selectivity of enclathration determined by competition experiments.     

水滑石类插层组装功能材料

水滑石类(LDHs)化合物是一类典型的阴离子型层状材料。LDHs的构筑单元和结构的可控性和多样性,为此类材料的应用研究提供了广阔前景。以LDHs的层状结构和可插层性为线索,介绍了LDHs的结构特征和制备化学,讨论了阴离子插层LDHs的组装原理和主-客体相互作用,对基于主体层板调控及主-客体相互作用的多种插层LDHs功能材料的制备和应用进行了综述,并对LDHs的结构创新和制备技术的研究方向进行了展望。