Tetraphenylethene‐Based Conjugated Fluoranthene: A Potential Fluorescent Probe for Detection of Nitroaromatic Compounds

This study reports the synthesis and photophysical properties of a star‐shaped, novel, fluoranthene–tetraphenylethene (TFPE) conjugated luminogen, which exhibits aggregation‐induced blue‐shifted emission (AIBSE). The bulky fluoranthene units at the periphery prevent intramolecular rotation (IMR) of phenyl rings and induces a blueshift with enhanced emission. The AIBSE phenomenon was investigated by solvatochromic and temperature‐dependent emission studies. Nanoaggregates of TFPE, formed by varying the water/THF ratio, were investigated by SEM and TEM and correlated with optical properties. The TFPE conjugate was found to be a promising fluorescent probe towards the detection of nitroaromatic compounds (NACs), especially for 2,4,6‐trinitrophenol (PA) with high sensitivity and a high Stern–Volmer quenching constant. The study reveals that nanoaggregates of TFPE formed at 30 and 70 % water in THF showed unprecedented sensitivity with detection limits of 0.8 and 0.5 ppb, respectively. The nanoaggregates formed at water fractions of 30 and 70 % exhibit high Stern–Volmer constants (K_sv=79 998 and 51 120 m ^?1, respectively) towards PA. Fluorescence quenching is ascribed to photoinduced electron transfer between TFPE and NACs with a static quenching mechanism. Test strips coated with TFPE luminogen demonstrate fast and ultra‐low‐level detection of PA for real‐time field analysis.     

Overcoming the Inhibition Effects of Citrate: Precipitation of Ferromagnetic Magnetite Nanoparticles with Tunable Morphology,Magnetic Properties,and Surface Charge via Ferrous Citrate Oxidation

This study demonstrates how the method of thermally assisted oxidative precipitation in water can be opened for—the so far neglected—metal organic iron(II) complexes (herein: citrate) in order to obtain, in one step, ferromagnetic magnetite nanoparticles, possessing essential ligand properties. Based on a dedicated analysis of the specific precursor in combination with the consideration of known properties of the ligand, it is possible to identify existing inhibition-attributes of the iron organyl such that these can be overcome. Moreover, they can be exploited in a targeted manner; thus, simply by changing concentrations, a variety of magnetite nanoparticle morphologies with distinct properties can be obtained. In the case of the herein investigated ferrous citrate, three major inhibition effects are identified. While two of them efficiently prevent the formation of magnetite and need to be addressed to be overcome, the third can be exploited to selectively synthesize, for example, relatively stable carboxyl group-bearing nuclei clusters, exhibiting the properties of magnetically responsive photonic crystals, or relatively large mesocrystals, whose intraparticular magnetic interactions are apparently disturbed.     

Implicit–explicit schemes for nonlinear nonlocal equations with a gradient flow structure in one space dimension

Nonlinear convection–diffusion equations with nonlocal flux and possibly degenerate diffusion arise in various contexts including interacting gases, porous media flows, and collective behavior in biology. Their numerical solution by an explicit finite difference method is costly due to the necessity of discretizing a local spatial convolution for each evaluation of the convective numerical flux, and due to the disadvantageous Courant–Friedrichs–Lewy (CFL) condition incurred by the diffusion term. Based on explicit schemes for such models devised in the study of Carrillo et al. a second‐order implicit–explicit Runge–Kutta (IMEX‐RK) method can be formulated. This method avoids the restrictive time step limitation of explicit schemes since the diffusion term is handled implicitly, but entails the necessity to solve nonlinear algebraic systems in every time step. It is proven that this method is well defined. Numerical experiments illustrate that for fine discretizations it is more efficient in terms of reduction of error versus central processing unit time than the original explicit method. One of the test cases is given by a strongly degenerate parabolic, nonlocal equation modeling aggregation in study of Betancourt et al. This model can be transformed to a local partial differential equation that can be solved numerically easily to generate a reference solution for the IMEX‐RK method, but is limited to one space dimension.     

Exciton Interactions,Excimer Formation,and [2π+2π] Photodimerization in Nonconjugated Curcuminoid-BF2 Dimers

We describe the synthesis of a series of covalently linked dimers of quadrupolar curcuminoid-BF₂ dyes and the detailed investigation of their solvent-dependent spectroscopic and photophysical properties. In solvents of low polarity, intramolecular folding induces the formation of aggregated chromophores, the UV/Vis absorption spectra of which display the optical signature characteristic of weakly-coupled H-aggregates. The extent of folding and, in turn, of ground-state aggregation is strongly dependent on the nature of the flexible linker. Steady-state and time-resolved fluorescence emission spectroscopies show that the Frenkel exciton relaxes into a fluorescent symmetrical excimer state with a long lifetime. Furthermore, our in-depth studies show that a weakly emitting excimer lies on the pathway toward a photocyclomer. Two-dimensional ¹H NMR spectroscopy and density functional theory (DFT) allowed the structure of the photoproduct to be established. To our knowledge, this represents the first example of a [2π+2π] photodimerization of the curcuminoid chromophore.     

Nucleation of Hematite: A Nonclassical Mechanism

Hematite (α-Fe₂O₃) is thermodynamically stable under ambient conditions, of vast geological importance, and widely used in applications, for example, as corrosion protection and as a pigment. It forms at elevated temperatures, whereas room-temperature reactions typically yield metastable akaganéite or ferrihydrite. The mechanistic key changes underlying this observation were explored in the present study. The entropic contribution to the prenucleation hydrolysis reaction categorically implies the presence of prenucleation clusters (PNCs) as fundamental precursors. The formation of hematite is then due to a change in the reaction mechanism above approximately 50 °C, whereby the reaction limitation towards oxolation in phase-separated clusters is overcome. A model that rationalizes the occurrence of hematite, akaganéite, and ferrihydrite based on the chemistry of olation PNCs is proposed. Supersaturation and the temperature dependence of olation and oxolation rates from monomeric precursors are irrelevant in this nonclassical mechanism.     

Stimuli-Responsive Fluorescent Nanoswitches: Solvent-Induced Emission Enhancement of Copper Nanoclusters

Copper nanoclusters (CuNCs) as a new class of fluorescent materials have attracted a great deal of interest due to their outstanding fluorescence properties. In this work, a variety of organic solvents were used to induce self-assembly of glutathione-capped CuNCs (GSH-CuNCs) to form ordered assemblies with enhanced fluorescence properties. Assemblies with multicolor fluorescence emission were constructed on the basis of the aggregation-induced emission (AIE) of GSH-CuNCs and the solvent effect. The fluorescence emission from these GSH-CuNCs assemblies can also be tuned from yellow to purple by changing the organic solvent. A possible mechanism based on the size of the assemblies and electron transfer was explored to explain the solvent effects on GSH-CuNCs. Stimuli-responsive nanoswitches with excellent reversibility can be controlled by changing the type of organic solvent and the ratio of the organic solvent to the aqueous solution of GSH-CuNCs. As the CuNCs assemblies exhibit strong, stable, and color-tunable fluorescence, they were employed as color-conversion materials for recognizing different organic solvents.     

Thermo‐ and pH‐sensitive triblock copolymers with tunable hydrophilic/hydrophobic properties

Polymers consisting of poly(acrylic acid) (PAA) and statistical poly[(acrylic acid)‐co‐(tert‐butylacrylate)] (P(AA‐co‐tBA)), attached to both extremities of Jeffamine® (D series based on a poly(propylene oxide) (PPO) with one amine function at each end) using atom transfer radical polymerization (ATRP) are presented in this article. An original bifunctional amide‐based macroinitiator was first elaborated from Jeffamine®. tBA polymerization was subsequently initiated from this macroinitiator. This polymerization occurs in a well‐controlled manner leading to narrow molecular weights distribution. Amphiphilic copolymers were finally obtained after complete or partial hydrolysis of the PtBA blocks into PAA. The control of the partial hydrolysis of tBA units, conducted in a concentrated HCl/tetrahydrofuran mixture, is demonstrated. The properties of the triblock copolymers were preliminary investigated in aqueous solution by absorbance, DLS measurements and SEC/MALS/DV/DRI analysis as a function of temperature and pH modifications, providing evidences of thermo‐ and pH‐sensitive self‐assembly of the copolymers. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2606–2616     

Immobilization of AIEgens into metal‐organic frameworks: Ligand design,emission behavior,and applications

Aggregation‐induced emission (AIE), in which the luminophores are highly emissive in aggregate state, is one of the most unique photophysical phenomena and has shown interesting applications in many areas. The immobilization of AIE luminogens (AIEgens) into metal‐organic frameworks (MOFs), which are inorganic‐organic hybrid porous materials with tunable and predictable structures, has been investigated over the past few years. These well‐defined porous frameworks cannot only provide an ideal platform for studying the mechanism of AIE phenomenon in solid state, but also show potential applications from sensing to white light‐emitting diodes. In this highlight, we will summarize the recent progress of AIEgens‐based MOFs, including ligand design, emission behavior, and applications. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 1809–1817