A novel mesoporous SBA-15 type of hybrid material (phen-SBA-15) covalently bonded with 1,10-phenanthroline (phen) ligand was synthesized by co-condensation of tetraethoxysilane (TEOS) and the chelate ligand 5-[N,N-bis-3-(triethoxysilyl)propyl]ureyl-1,10-phenanthroline (phen-Si) in the presence of Pluronic P123 surfactant as a template. The preservation of the chelate ligand structure during the hydrothermal synthesis and the surfactant extraction process was confirmed by Fourier transform infrared (FTIR) and (29)Si MAS NMR spectroscopies. SBA-15 consisting of the highly luminescent ternary complex Eu(TTA)(3)phen (TTA = 2-thenoyltrifluoroacetone) covalently bonded to a silica-based network, which was designated as Eu(TTA)(3)phen-SBA-15, was obtained by introducing the Eu(TTA)(3).2H(2)O complex into the hybrid materials via a ligand exchange reaction. XRD, TEM, and N(2) adsorption measurements were employed to characterize the mesostructure of Eu(TTA)(3)phen-SBA-15. For comparison, SBA-15 doped with Eu(TTA)(3).2H(2)O and Eu(TTA)(3)phen complexes and SBA-15 covalently bonded with a binary europium complex with phen ligand were also synthesized, and were named SBA-15/Eu(TTA)(3), SBA-15/Eu(TTA)(3)phen, and Eu-phen-SBA-15, respectively. The detailed luminescence studies on all the materials showed that, compared with the doping sample SBA-15/Eu(TTA)(3)phen and binary europium complex functionalized sample Eu-phen-SBA-15, the Eu(TTA)(3)phen-SBA-15 mesoporous hybrid material exhibited higher luminescence intensity and emission quantum efficiency. Thermogravimetric analysis on Eu(TTA)(3)phen-SBA-15 demonstrated that the thermal stability of the lanthanide complex was evidently improved as it was covalently bonded to the mesoporous SBA-15 matrix.

Stimuli‐responsive photoluminescent materials have attracted considerable attention owing to their potential applications in security protection because the information recorded directly in materials with static luminescent outputs are usually visible under either ambient or UV light. Herein, we realize reversible information anticounterfeiting by loading a photoswitchable diarylethene derivative into a lanthanide metal–organic framework (MOF). Light triggers the open‐ and closed‐form isomerization of the diarylethene unit, which respectively regulates the inactivation and activation of the photochromic FRET process between the diarylethene acceptor and lanthanide donor, resulting in reversible luminescence on–off switching of the lanthanide emitting center in the MOF host. This photoresponsive host–guest system allows for reversible multiple information pattern visible/invisible transformation by simply alternating the exposure to UV and visible light.

Photoluminescent soft materials have been widely applied in sensing, display devices, and organic light-emitting diodes, [1] and also have received great attention toward security protection applications in information storage, date recording and encryption. [2] In particular, luminescent hydrogel-based 3D codes prepared in environmentally friendly process could not only increase the information density per unit area but also be employed as wearable or biological anti-counterfeiting materials. [3] On the other hand, the information recorded directly in these materials is usually visible under either ambient or UV light, which would hamper their practical applications in confidential information protection because these anti-counterfeiting labels could be easily mimicked. [4] In this context, smart luminescent materials that can perceive the surrounding stimuli and respond to them should be ideal for confidential information protection. [5] Under external stimuli, the luminescent outputs of these materials can be precisely modulated, preventing the information from being stolen or mimicked. [6,7] Stimulus-responsive luminescent materials that rely on constant addition of chemicals have been developed for information encryption and decryption. [8] Since these methods require invasive stimuli, it may be difficult for consumers without professional chemistry knowledge to handle the encoded information by adding chemicals. Therefore, it is highly desirable to develop alternative switchable luminescent materials with confidential encryption property capable of being easily operated in a noninvasive manner, where the security codes are initially invisible and become visible under specific external stimuli. In this way, reversible information encryption and decryption could be achieved. Light irradiation is an appealing external stimulus because it provides clean, spatiotemporal, and noninvasive control on the operation with high precision, [9] showing greater convenience in activating or erasing the code information as compared to other chemical stimuli. [10] In terms of emitting sources, lanthanide complexes are excellent emitting centers because of their intriguing optical properties, such as narrow emission bands, large Stokes shift, high luminescent efficiency, and long luminescence lifetime. [7,11] To the best of our knowledge, however, achieving Conventional luminescent information is usually visible under either ambient or UV light, hampering their potential application in smart confidential information protection. In order to address this challenge, herein, light-triggered luminescence ON-OFF switchable hybrid hydrogels are successfully constructed through in situ copolymerization of acrylamide, lanthanide complex, and diarylethene photochromic unit. The open-close behavior of the diarylethene ring in the polymer could be controlled by UV and visible light irradiation, where the close form of the ring features fluorescence resonance energy transfer with the lanthanide complex. The hydrogel-based block...

Our data suggested that circulating miRNAs could serve as biomarkers for CaP, and compared to single miRNA, the 5 miRNAs panel can accurately discriminate CaP from BPH and healthy controls with high sensitivity and specificity, and therefore, combined with routine PSA test, these 5 CaP-specific miRNAs may help improve CaP diagnosis in clinical application.

Aluminum salen complexes bearing appended quaternary ammonium salt substituents have been synthesized and shown to be effective catalysts for the coupling of epoxides and carbon dioxide to generate cyclic carbonates. 27 Al NMR spectra have demonstrated that these exist as both five-and six-coordinate Al(III) species in dimethylsulfoxide (DMSO) solution, whereas only a five-coordinate Al(III) species was detected in the (salen)AlCl analogue in the presence of an external onium salt. The onium salt group tethered on the salen ligand was found to play an important role in enhancing the catalytic activity. The effects of reaction variables such as temperature, time, pressure, molar ratio of epoxide to catalyst on the catalytic performance were systematically investigated. These bifunctional catalysts were found to be highly stable to moisture and oxygen, resistant to impurities, and recyclable with only minor losses in catalytic activity.

We discuss artificial photonic antenna systems that are built by incorporating chromophores into one-dimensional nanochannel materials and by organizing the latter in specific ways. Zeolite L (ZL) is an excellent host for the supramolecular organization of different kinds of molecules and complexes. The range of possibilities for filling its one-dimensional channels with suitable guests has been shown to be much larger than one might expect. Geometrical constraints imposed by the host structure lead to supramolecular organization of the guests in the channels. The arrangement of dyes inside the ZL channels is what we call the first stage of organization. It allows light harvesting within the volume of a dye-loaded ZL crystal and also the radiationless transport of energy to either the channel ends or center. One-dimensional FRET transport can be realized in these guest-host materials. The second stage of organization is realized by coupling either an external acceptor or donor stopcock fluorophore at the ends of the ZL channels, which can then trap or inject electronic excitation energy. The third stage of organization is obtained by interfacing the material to an external device via a stopcock intermediate. A possibility to achieve higher levels of organization is by controlled assembly of the host into ordered structures and preparation of monodirectional materials. The usually strong light scattering of ZL can be suppressed by refractive-index matching and avoidance of microphase separation in hybrid polymer/dye-ZL materials. The concepts are illustrated and discussed in detail on a bidirectional dye antenna system. Experimental results of two materials with a donor-to-acceptor ratio of 33:1 and 52:1, respectively, and a three-dye system illustrate the validity and challenges of this approach for synthesizing dye-nanochannel hybrid materials for light harvesting, transport, and trapping.

While photoluminescence printing is a widely applied anticounterfeiting technique, there are still challenges in developing new generation anticounterfeiting materials with high security. Here we report the construction of a photoresponsive supramolecular coordination polyelectrolyte (SCP) through hierarchical self-assembly of lanthanide ion, bis-ligand and diarylethene unit, driven by metal-ligand coordination and ionic interaction. Owing to the conformation-dependent photochromic fluorescence resonance energy transfer between the lanthanide donor and diarylethene acceptor, the ring-closure/ring-opening isomerization of the diarylethene unit leads to a photoreversible luminescence on/off switch in the SCP. The SCP is then utilized as security ink to print various patterns, through which photoreversible multiple information patterns with visible/invisible transformations are realized by simply alternating the irradiation with UV and visible light. This work demonstrates the possibility of developing a new class of smart anticounterfeiting materials, which could be operated in a noninvasive manner with a higher level of security.

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