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Principles Of Fluorescence Spectroscopy

Functional π-Gelators and Their Applications

Over the past few years, there has been a great deal of interest in the development of hydrogel materials with tunable structural, mechanical, and rheological properties, which exhibit rapid and autonomous self-healing and self-recovery for utilization in a broad range of applications, from soft robotics to tissue engineering. However, self-healing hydrogels generally either possess mechanically robust or rapid self-healing properties but not both. Hence, the development of a mechanically robust hydrogel material with autonomous self-healing on the time scale of seconds is yet to be fully realized. Here, the current advances in the development of autonomous self-healing hydrogels are reviewed. Specifically, methods to test self-healing efficiencies and recoveries, mechanisms of autonomous self-healing, and mechanically robust hydrogels are presented. The trends indicate that hydrogels that self-heal better also achieve self-healing faster, as compared to gels that only partially self-heal. Recommendations to guide future development of self-healing hydrogels are offered and the potential relevance of self-healing hydrogels to the exciting research areas of 3D/4D printing, soft robotics, and assisted health technologies is highlighted.

Self-Healing Hydrogels

Detection Ying Zhou,†,‡ Jun Feng Zhang, and Juyoung Yoon*,† †Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea ‡Key Laboratory of Medicinal Chemistry for Natural Resource, School of Chemical Science and Technology, Yunnan University, Kunming, 650091, P. R. China College of Chemistry and Chemical Engineering, Yunnan Normal University, Kunming 650500, P. R. China

Fluorescence and colorimetric chemosensors for fluoride-ion detection.

Fogging occurs when moisture condensation takes the form of accumulated droplets with diameters larger than 190 nm or half of the shortest wavelength (380 nm) of visible light. This problem may be effectively addressed by changing the affinity of a material’s surface for water, which can be accomplished via two approaches: i) the superhydrophilic approach, with a water contact angle (CA) less than 5°, and ii) the superhydrophobic approach, with a water CA greater than 150°, and extremely low CA hysteresis. To date, all techniques reported belong to the former category, as they are intended for applications in optical transparent coatings. A well-known example is the use of photocatalytic TiO2 nanoparticle coatings that become superhydrophilic under UV irradiation. Very recently, a capillary effect was skillfully adopted to achieve superhydrophilic properties by constructing 3D nanoporous structures from layer-by-layer assembled nanoparticles. The key to these two “wet”-style antifogging strategies is for micrometer-sized fog drops to rapidly spread into a uniform thin film, which can prevent light scattering and reflection from nucleated droplets. Optical transparency is not an intrinsic property of antifogging coatings even though recently developed antifogging coatings are almost transparent, and the transparency could be achieved by further tuning the nanoparticle size and film thickness. To our knowledge, the antifogging coatings may also be applied to many fields that do not require optical transparency, including, for example, paints for inhibiting swelling and peeling issues and metal surfaces for preventing corrosion. These types of issues, which are caused by adsorption of moisture, are hard to solve by the superhydrophilic approach because of its inherently “wet” nature. Thus, a “dry”-style antifogging strategy, which consists of a novel superhydrophobic technique that can prevent moisture or microscale fog drops from nucleating on a surface, is desired. Recent bionic researches have revealed that the self-cleaning ability of lotus leaves and the striking ability of a water-strider’s legs to walk on water can be attributed to the ideal superhydrophobicity of their surfaces, induced by special microand nanostructures. To date, the biomimetic fabrication of superhydrophobic microand/or nanostructures has attracted considerable interest, and these types of materials can be used for such applications as self-cleaning coatings and stain-resistant textiles. Although a superhydrophobic technique inspired by lotus leaves is expected to be able to solve such fogging problems because the water droplets can not remain on the surface, there are no reports of such antifogging coatings. Very recently, researchers from General Motors have reported that the surfaces of lotus leaves become wet with moisture because the size of the fog drops are at the microscale—so small that they can be easily trapped in the interspaces among micropapillae. Thus, lotuslike surface microstructures are unsuitable for superhydrophobic antifogging coatings, and a new inspiration from nature is desired for solving this problem. In this communication, we report a novel, biological, superhydrophobic antifogging strategy. It was found that the compound eyes of the mosquito C. pipiens possess ideal superhydrophobic properties that provide an effective protective mechanism for maintaining clear vision in a humid habitat. Our research indicates that this unique property is attributed to the smart design of elaborate microand nanostructures: hexagonally non-close-packed (ncp) nipples at the nanoscale prevent microscale fog drops from condensing on the ommatidia surface, and hexagonally close-packed (hcp) ommatidia at the microscale could efficiently prevent fog drops from being trapped in the voids between the ommatidia. We also fabricated artificial compound eyes by using soft lithography and investigated the effects of microand nanostructures on the surface hydrophobicity. These findings could be used to develop novel superhydrophobic antifogging coatings in the near future. It is known that mosquitoes possess excellent vision, which they exploit to locate various resources such as mates, hosts, and resting sites in a watery and dim habitat. To better understand such remarkable abilities, we first investigated the interaction between moisture and the eye surface. An ultrasonic humidifier was used to regulate the relative humidity of the atmosphere and mimic a mist composed of numerous tiny water droplets with diameters less than 10 lm. As the fog was C O M M U N IC A IO N

The dry-style antifogging properties of mosquito compound eyes and artificial analogues prepared by soft lithography: a superhydrophobic state with high adhesive force

Novel strategy for the environmentally benign bulk level synthesis of nickel nanoparticles.

Integrating thermodynamics towards bulk level synthesis of nano Ni catalysts: a green mediated sol–gel auto combustion method

To push the boundary of the efficiency of perovskite nanocrystal-based photovoltaics, understanding the charge transfer at the interface of these nanocrystals is necessary. In an effort to understand the electronic effects of the substituents in the charge acceptor moiety, three electronically different small molecules (namely, chloranilic acid (CA), p-benzoquinone (BQ), and duroquinone (DQ)) were chosen and their detailed charge transfer dynamics were studied at the CsPbBr3 perovskite nanocrystal-small organic molecule interface using steady state and time-resolved spectroscopic methods. The steady-state absorption and time-resolved emission studies reveal that all three molecules interact with the NCs in the excited state. Femtosecond transient absorption experiments indicate a faster ground-state bleach recovery in the presence of the three acceptors, compared with the pristine NCs. Utilizing band alignment analysis, the faster bleach recovery of the NCs in presence of the acceptors was confirmed to be because of electron transfer from the photo-excited NCs to the acceptor molecules. Moreover, the electron transfer rates fall in the Marcus normal region and can be explained based on the electronic effects of the substituents present on the acceptor molecules.

Electronic effect of substituents on the charge-transfer dynamics at the CsPbBr3 perovskite-small molecule interface.

Synthesis of electrically conducting and thermally stable photoluminescent anthracene nanorods

A pyrene-based highly emissive low-molecular-weight organogelator, [2-(4-fluorophenyl)-3-(pyren-1-yl)acrylonitrile] (F1), is presented, which divulges thixotropic and thermochromic fluorescence switching via reversible gel-to-sol transition and tremendous superhydrophobicity (mean contact angles: 149-160°), devoid of any gelling and/or hydrophobic units. The rationale for the design strategy reveals that the restricted intramolecular rotation (RIR) in J-type self-assembly promotes F1 for the prolific effects of aggregation- and gelation-induced enhanced emission (AIEE and GIEE). Meanwhile, hindrance in charge transfer via the nucleophilic reaction of cyanide (CN-) on the C═C unit in F1 facilitates the selective fluorescence "turn-on" response in both solution [9:1 (v/v) DMSO/water] and solid state [paper kits] with significantly lower detection limits (DLs) of 37.23 nM and 13.4 pg/cm2, respectively. Subsequently, F1 discloses CN- modulated colorimetric and fluorescence "turn-off" dual-channel response for aqueous 2,4,6-trinitrophenol (PA) and 2,4-dinitrophenol (DNP) in both solution (DL = 49.98 and 44.1 nM) and solid state (DL = 114.5 and 92.05 fg/cm2). Furthermore, the fluorescent nanoaggregates of F1 in water and its xerogel films permit a rapid dual-channel "on-site" detection of PA and DNP, where the DLs ranged from nanomolar (nM) to sub-femtogram (fg) levels. Mechanistic insights reveal that the ground-state electron transfer from the fluorescent [F1-CN] ensemble to the analytes is responsible for anion driven sensory response, whereas the unusual inner filter effect (IFE) driven photoinduced electron transfer (PET) was responsible for self-assembled F1 response toward desired analytes. Additionally, the nanoaggregates and xerogel films also detect PA and DNP in their vapor phase with reasonable percentage of recovery from the soil and river water samples. Therefore, the elegant multifunctionality from a single luminogenic framework allows F1 to provide a smart pathway for achieving environmentally benign real-world applications on multiple platforms.

A Gelation-Induced Enhanced Emission Active Stimuli Responsive and Superhydrophobic Organogelator: "Turn-On" Fluorogenic Detection of Cyanide and Dual-Channel Sensing of Nitroexplosives on Multiple Platforms.

Bronsted acid-promoted straightforward synthesis of N-fused tricyclic angular imidazoquinolines in high yields is realized through a succinct 1,3-hydride shift. The protocol is operationally simple, scalable, and features broad scope. A photophysical study revealed that these π-extended imidazoquinolines display large Stokes shifts (up to 158 nm) and high fluorescent quantum yields.

Edamana Prasad

Papers

Integrating thermodynamics towards bulk level synthesis of nano Ni catalysts: a green mediated sol–gel auto combustion method

Electronic effect of substituents on the charge-transfer dynamics at the CsPbBr3 perovskite-small molecule interface.

Synthesis of electrically conducting and thermally stable photoluminescent anthracene nanorods

A Gelation-Induced Enhanced Emission Active Stimuli Responsive and Superhydrophobic Organogelator: "Turn-On" Fluorogenic Detection of Cyanide and Dual-Channel Sensing of Nitroexplosives on Multiple Platforms.

Brønsted Acid-promoted Facile Synthesis of N-Fused Angular Imidazoquinolines