Blue-to-UVB Upconversion, Solvent Sensitization and Challenging Bond Activation Enabled by a Benzene-Based Annihilator.

Several energy-demanding photoreactions require harsh UV light from inefficient light sources. The conversion of low-energy visible light to high-energy singlet states via triplet-triplet annihilation upconversion (TTA-UC) could offer a solution for driving such reactions under mild conditions. We present the first annihilator with an emission maximum in the UVB region that, combined with an organic sensitizer, is suitable for blue-to-UVB upconversion. The annihilator singlet was successfully employed as an energy donor in subsequent FRET activations of aliphatic carbonyls. This hitherto unreported UC-FRET reaction sequence was directly monitored using laser spectroscopy and applied to mechanistic irradiation experiments demonstrating the feasibility of Norrish chemistry. Our results provide clear evidence for a novel blue light-driven substrate or solvent activation strategy, which is important in the context of developing more sustainable light-to-chemical energy conversion systems.

Evolution of Artificial Arginine Analogues-Fluorescent Guanidiniocarbonyl-Indoles as Efficient Oxo-Anion Binders.

In this article, we present fluorescent guanidiniocarbonyl-indoles as versatile oxo-anion binders. Herein, the guanidiniocarbonyl-indole (GCI) and methoxy-guanidiniocarbonyl-indole (MGCI) were investigated as ethylamides and compared with the well-known guanidiniocarbonyl-pyrrole (GCP) concerning their photophysical properties as well as their binding behavior towards oxo-anions. Hence, a variety of anionic species, such as carboxylates, phosphonates and sulfonates, have been studied regarding their binding properties with GCP, GCI and MGCI using UV-Vis titrations, in combination with the determination of the complex stoichiometry using the Job method. The emission properties were studied in relation to the pH value using fluorescence spectroscopy as well as the determination of the photoluminescence quantum yields (PLQY). Density functional theory (DFT) calculations were undertaken to obtain a better understanding of the ground-lying electronic properties of the investigated oxo-anion binders. Additionally, X-ray diffraction of GCP and GCI was conducted. We found that GCI and MGCI efficiently bind carboxylates, phosphonates and sulfonates in buffered aqueous solution and in a similar range as GCP (Kass ≈ 1000-18,000 M-1, in bis-tris buffer, pH = 6); thus, they could be regarded as promising emissive oxo-anion binders. They also exhibit a visible fluorescence with a sufficient PLQY. Additionally, the excitation and emission wavelength of MGCI was successfully shifted closer to the visible region of the electromagnetic spectrum by introducing a methoxy-group into the core structure, which makes them interesting for biological applications.

Mapping the Regioisomeric Space and Visible Color Range of Purely Organic Dual Emitters with Ultralong Phosphorescence Components: From Violet to Red Towards Pure White Light.

We mapped the entire visible range of the electromagnetic spectrum and achieved white light emission (CIE: 0.31, 0.34) by combining the intrinsic ns-fluorescence with ultralong ms-phosphorescence from purely organic dual emitters. We realized small molecular materials showing high photoluminescence quantum yields (ΦL ) in the solid state at room temperature, achieved by active exploration of the regioisomeric substitution space. Chromophore stacking-supported stabilization of triplet excitons with assistance from enhanced intersystem crossing channels in the crystalline state played the primary role for the ultra-long phosphorescence. This strategy covers the entire visible spectrum, based on organic phosphorescent emitters with versatile regioisomeric substitution patterns, and provides a single molecular source of white light with long lifetime (up to 163.5 ms) for the phosphorescent component, and high overall photoluminescence quantum yields (up to ΦL =20 %).

Bridged Aromatic Oxo- and Thioethers with Intense Emission in Solution and the Solid State.

In this contribution, we report on a class of emitters based on bridged oxo- and/or thioethers revealing striking photoluminescence properties in fluid solution and in the solid state. In total, nine compounds were investigated concerning their photophysical properties, which were interpreted by quantum chemical calculations. To our delight, we discovered compounds possessing nearly identical photoluminescence quantum yields (ΦF ) in solution and in the solid state, which has been rarely reported so far. Besides these efforts, we shed light on the influence of polymorphism and solvent polarity on the emission properties. In addition, an in-depth X-ray diffractometric analysis was conducted to correlate molecular packing in the crystal with differences in the photophysical properties.

Tuning the solid-state emission of liquid crystalline nitro-cyanostilbene by halogen bonding.

The first example of halogen-bonded fluorescent liquid crystals based on the interaction of iodofluorobenzene derivatives with nitro-cyanostilbenes is reported. The systematic variation of the fluorination degree and pattern indicates the relevance of the halogen bond strength for the induction of liquid crystalline properties. The modular self-assembly approach enables the efficient tuning of the fluorescence behaviour and mesomorphic properties of the assemblies.

All in One: Stimuli-Responsive, Efficient Mitotracking, and Single Source White Light Emission.

"All in one" type luminogens, possessing combined properties related to optical, materials, and biological implications, are of urgent demand today, mainly because of the combined application potential of such probes. To the best of our knowledge, until now, an "all in one" type white light emitter together with stimuli-responsive behavior and highly efficient mitochondrial-tracking ability has not been reported yet. In this contribution, for the first time, we have investigated a pair of luminogens exhibiting white light emission (CIE coordinates: 0.35, 0.35 (DPAEOA) and 0.29, 0.33 (DPAPMI)) with temperature-induced mechanochromic features of a centrosymmetrically packed probe (space group P-1). Most importantly, despite being neutral, our designed probe DPAEOA can specifically illuminate mitochondria with the highest Pearson coefficient value (0.93), which is rare, as almost all the commercially developed mitotrackers are cationic fluorophores. Thus, this study will pave a new avenue for the design of next generation "all in one" type organic luminogens exhibiting potential applications in notable optical, materials, and biological fields.

Sensing and modulation of amyloid fibrils by photo-switchable organic dots.

Abnormal aggregation of amyloidogenic proteins (like Aß 42, amylin, α-synuclein, insulin) and the deposition of these aggregates is believed to be associated with several diseases known as amyloidosis. The pathway of aggregation involves three distinct phases: the oligomeric, elongation and plateau phases. Among them, the oligomeric phase of Aß 42 and α-synuclein involves the generation of transient oligomeric species suspected to cause several neurological disorders, including Alzheimer's and Parkinson's diseases. Over the past few years, scientists have devoted much more effort to devising new fluorescent molecular probes to estimate the mechanisms of formation, and have gained vital information about possible therapeutic routes for amyloidosis. However, such fluorescent probes face serious limitations because of self-quenching at high concentrations of the probe; therefore, they are inappropriate for quantitative analysis and bio-imaging experiments. Hence, smart biocompatible fluorescent probes are indispensable, as they not only overcome the drawbacks of conventional fluorescent probes, but also have the potential ability to fight amyloidosis through modulation of the pathways involved. In this work, for the first time we introduce a series of promising photo-switchable aggregation-induced emission (AIE) dots (DPAPMI, CPMI) and aggregation caused quenching (ACQ) dots (DMAPMI) which can detect amyloid fibrils in terms of switching and enhancing their fluorescence emission. Interestingly, the organic dots enhance the aggregation rate of insulin by speeding up the microscopic processes, specifically secondary nucleation (with rate constant k2) and the elongation process (with rate constant k+). Moreover, the comparison of kinetics studies with ThT suggests that our organic dots can sense pre-fibrillar aggregates of insulin during the aggregation process, which may be beneficial for the early detection of amyloid fibrils. In summary, our study indicates that these organic dots can be used for the imaging and early stage detection of amyloid fibril formation and the modulation of amyloid formation pathways.

Impact of Topology on the Characteristics of Water inside Cubic Lyotropic Liquid Crystalline Systems.

Water molecules present inside the lipid-based cubic liquid crystalline phases are found to play a major role in wide range of applications, such as protein crystallization, virus detection, delivery of drug and biomolecules, etc. In this regard, it is crucial to elucidate static and dynamic properties of the water molecules in the nanochannels and to explore the effect of geometrical topology on the nature of the water inside the different cubic phases. In the present work, we have incorporated two probes, coumarin-343 (C-343) and coumarin-480 (C-480), in two cubic phases with different symmetries, namely gyroid ( Ia3 d) and double diamond ( Pn3 m) with the same water content (22%), to probe the micropolarity, the microviscosity, and the hydration dynamics at different hydrophobic depths in the mesophases. Steady state results estimate the polarity at the lipid-water interface to be similar to that of ethanol, and the polarity near the more hydrophilic parts of the nanochannel resembles that of ethylene glycol. We have also observed a gradient in the microviscosity inside the LLC nanochannels from time-resolved fluorescence anisotropy studies. The hydration dynamics, which play a key role in the numerous applications of the mesophases, have been probed by the time-dependent Stokes shift method of the two probes, revealing the existence of three kinds of dynamics. The difference in the hydration dynamics inside the two mesophases, where the water molecules confined in the Ia3 d phase exhibit a slower dynamics compared to that in Pn3 m, is the prime importance of this work. The underlying reason for this disparity is majorly associated with the differences in the topology of the two structures including the hydrophobic packing stress, the negative interfacial curvature, and the curvature elastic energy of the lipid-water interface. We believe that this kind of correlation between the structural topology of the different cubic LLC mesophases and nature of the water nanochannel will help to boost the applications of the cubic phases in the future.

Conformational and solution dynamics of hemoglobin (Hb) in presence of a cleavable gemini surfactant: Insights from spectroscopy, atomic force microscopy, molecular docking and density functional theory.

Herein, we have explored the conformational alterations of hemoglobin (Hb) in presence of a cleavable gemini surfactant (C16-C4O2-C16). The concerned surfactant was found to induce significant structural perturbations in Hb. UV-vis spectroscopy, steady-state/time-resolved fluorescence, and other utilized techniques have authenticated the complexation of Hb with the gemini surfactant. CD has demonstrated the alterations in secondary structural elements (α-helicity, ß-sheet, ß-turn, and random coil) of Hb upon C16-C4O2-C16 addition. Atomic force microscopy (AFM) has revealed the existence of unique star-shaped gemini surfactant microstructures aligned to Hb in a necklace pattern. The 1H NMR peak broadening and lower delta values hint at the binding of the concerned gemini surfactant to Hb. Molecular docking and DFT calculations have further substantiated the Hb-gemini complex formation and the involvement of electrostatic/hydrophobic forces therein. In future, these results might pave-the-way to construct self-assembled, sustainable, and green surfactant-protein mixtures for their end-use in industrial, engineering, biomedical, drug delivery, gene transfection, and other relevant excipient formulations.

Anthracene-Resorcinol Derived Covalent Organic Framework as Flexible White Light Emitter.

The ordered modular structure of a covalent organic framework (COF) facilitates the selective incorporation of electronically active segments that can be tuned to function cooperatively. This designability inspires developing COF-based single-source white light emitters, required in next-generation solid-state lighting. Here, we present a new anthracene-resorcinol-based COF exhibiting white light emission. The keto-enol tautomers present in the COF give rise to dual emission, which can be tuned by the O-donor and N-donor solvents. Importantly, when suspended in a solid polymer matrix, this dual emission is retained as both tautomers coexist. A mere 0.32 wt % loading of the COF in poly(methyl methacrylate) (PMMA) gives a solvent-free film with intense white light emission (CIE coordinates (0.35, 0.36)). From steady-state and time-resolved studies, the mechanism of the white light emission has been unambiguously assigned to fluorescence, with the blue emission originating from the π-stacked columns of anthracene, and the mixture of red and green from the keto-enol tautomerized resorcinol units. The study introduces the COF as a new class of readily processable, single-source white light emitter.

Developing the structure-property relationship to design solid state multi-stimuli responsive materials and their potential applications in different fields.

Prediction of multi-stimuli responsive behavior in newly developed luminogens is an appealing yet challenging puzzle, since no concrete design strategy has been developed so far. In this article, we demonstrate a potent strategy to gain a deep understanding of the structure-property relationship to design multi-stimuli responsive mechanochromic materials. To achieve our goal, a variety of new isoindolinone core based charge transfer luminogens exhibiting aggregation-induced emission (AIE) have been prepared through C-H bond activation using a cost-effective ruthenium (Ru) metal catalyzed one-pot synthetic strategy. We have shown that slight tuning of the donor moiety is found to be highly effective in controlling molecular packing and metastable energy states in solid states, and thus, optical properties and multi-stimuli responsive behaviors. The flexibility and twisting of donor moieties afford a loosely bound 'herringbone' packing, enabling reversible transformation under multiple mechanical stimuli. The cyclized derivative of the donor exhibits a completely different packing mode (i.e., cross packing), and subsequently, does not give rise to mechanochromism. The Hirshfeld surface analysis from a single crystal infers that non-covalent interactions (specifically C-H···π and π···π) are extremely important to yield mechanochromism under external force. Correlating all solid-state behavior with the molecular structure, we conclude that the synergistic effect between the twisting and conformational flexibility of donor moieties along with numerous non-covalent interactions gives rise to multi-stimuli responsive behaviors. Finally, the newly designed molecules are found to be highly emissive in solution and potentially applicable in fluorescence thermometer construction, lighting up cells, acid-base sensors and rewritable devices.

Solution behaviour of lysozyme in the presence of novel biodegradable gemini surfactants.

Extensive applications of biomacromolecule-surfactant mixtures in cosmetics, industry, agriculture, laundry and biomedical realms have raised environmental and ecological issues. Therefore, scientists now-a-days are concerned to design environmentally benevolent surfactant-protein mixtures which are not only efficient, but ecological too. In this context, we have studied the solution behaviour of hen egg white lysozyme (HEWL) in the presence of two novel biodegradable gemini surfactants by utilizing various spectroscopic and computational methods. The results confirmed the complex formation between Cm-E2O-Cm and HEWL via static mechanism and hydrophobic forces were found to be major contributing forces during interactions. C12-E2O-C12 was found to bind strongly to HEWL than C14-E2O-C14, owing to its smaller size and better penetration efficacy into the hydrophobic domains of HEWL. Upon Cm-E2O-Cm addition, conformational/microenvironmental alterations in HEWL were revealed, respectively, by circular dichroism and pyrene micro-polarity studies. Molecular modeling demonstrates that Cm-E2O-Cm binds in the locality of aromatic residues (Trp/Tyr). This study in future may lend a hand in designing safe and environmentally green surfactant-protein mixtures for their ultimate exploitation in food, laundry, and agriculture prefecture.

Topological Influence of Lyotropic Liquid Crystalline Systems on Excited-State Proton Transfer Dynamics.

In the present work, we have investigated the excited-state proton transfer (ESPT) dynamics inside lipid-based reverse hexagonal (HII), gyroid Ia3d, and diamond Pn3m LLC phases. Polarized light microscopy (PLM) and small-angle X-ray scattering (SAXS) techniques have been employed for the characterization of LLC systems. Time-resolved fluorescence results reveal the retarded ESPT dynamics inside liquid crystalline systems compared to bulk water, and it follows the order HII < Ia3d < Pn3m < H2O. The slower solvation, hampered "Grotthuss" proton transfer process, and most importantly, topological influence, of the LLC systems are believed to be mainly responsible for the slower and different extent of ESPT dynamics. Interestingly, recombination dynamics is found to be faster with respect to bulk water and it follows the order H2O < Pn3m < Ia3d < HII. Faster recombination dynamics arises due to lower dielectric constant and different channel diameters of these LLC systems. However, the dissociation dynamics is found to be slower than bulk water and it follows the order HII < Ia3d < Pn3m < H2O. Differences in critical packing parameter of LLC systems are believed to be the governing factors for the slower dissociation dynamics in these liquid crystalline systems.

Solvation Dynamics in Different Phases of the Lyotropic Liquid Crystalline System.

Reverse hexagonal (HII) liquid crystalline material based on glycerol monooleate (GMO) is considered as a potential carrier for drugs and other important biomolecules due to its thermotropic phase change and excellent morphology. In this work, the dynamics of encapsulated water, which plays important role in stabilization and formation of reverse hexagonal mesophase, has been investigated by time dependent Stokes shift method using Coumarin-343 as a solvation probe. The formation of the reverse hexagonal mesophase (HII) and transformation to the L2 phase have been monitored using small-angle X-ray scattering and polarized light microscopy experiments. REES studies suggest the existence of different polar regions in both HII and L2 systems. The solvation dynamics study inside the reverse hexagonal (HII) phase reveals the existence of two different types of water molecules exhibiting dynamics on a 120-900 ps time scale. The estimated diffusion coefficients of both types of water molecules obtained from the observed dynamics are in good agreement with the measured diffusion coefficient collected from the NMR study. The calculated activation energy is found to be 2.05 kcal/mol, which is associated with coupled rotational-translational water relaxation dynamics upon the transition from "bound" to "quasi-free" state. The observed ∼2 ns faster dynamics of the L2 phase compared to the HII phase may be associated with both the phase transformation as well as thermotropic effect on the relaxation process. Microviscosities calculated from time-resolved anisotropy studies infer that the interface is almost ∼22 times higher viscous than the central part of the cylinder. Overall, our results reveal the unique dynamical features of water inside the cylinder of reverse hexagonal and inverse micellar phases.