Fluorescent Aggregates Research Articles

A Simple Mannose-Coated Poly (p-Phenylene Ethynylene) for Qualitative Bacterial Capturing.

A mannose-functionalized poly (p-phenylene ethynylene) was rationally designed to achieve selective detection of bacteria. The polymer was constructed as a signaling unit and was modified by attaching aminoethyl mannose using the carboxylic acid group at the end of the linker. Incubation of Escherichia coli with the polymer yielded fluorescent bacteria aggregates through polyvalent interactions. The utility of the mannose functionalized polymer to detect E. coli expressing functional FimH mannose-specific lectin on their surface was also demonstrated. The sugar units displayed on the surface of the polymer retained their functional ability to interact with mannose-binding lectin. To determine the optimum binding time, we measured the fluorescence intensity of the polymer-bacteria suspension at intervals. Our results showed that binding in this system will reach an optimum level within 30 min of incubation. The polymer’s affinity for bacteria has been demonstrated and bacteria with a concentration of 103 CFU mL−1 can be detected by this system.

Facile construction of terpridine-based metallo-polymers in hydrogels, crystals and solutions directed by metal ions

Driven by tunable metal-ligand interactions, a polydentate ligand TC containing terpyridine and carboxylic acid units was developed to construct metallo-polymers that showed multiple aggregation modes with controlled macroscopic properties. In the presence of different kind of Zn2+ ions or NaOH, TC could form metallo-polymers via π-π stacking and metal-ligand interaction that further trapped water molecules, resulting in hydrogels and crystals. Moreover, these TC/Zn2+ hydrogels could transform to soluble and fluorescent aggregates in the presence of NaOH due to the formation of binuclear metallo-polymers with enhanced ICT emission. The metal-ligand interactions tuned by different metal salts in gels, crystals, and sols were also studied and illustrated in detail, it was also proved that water was an essential linker for constructing Na+-based metallo-polymers from the TC/NaOH crystal data. This work demonstrated the engineered coordination pathways in generating controllable hydrogels and metallo-polymers for the first time, which led to novel approach for facilely constructing a number of hydrogels with tailorable macroscopic properties.

Self-Assembling of Fmoc-GC Peptide Nucleic Acid Dimers into Highly Fluorescent Aggregates.

The study of molecules that self-assemble through noncovalent interactions is one of the most attractive topics in supramolecular chemistry. The use of short peptides or modified nucleotides as building blocks for the aggregates is particularly intriguing because these are very easy to synthesize; moreover, subtle changes in the chemical structure of such building blocks may drastically affect the properties of the aggregates. The ability of peptide nucleic acids (PNA) to aggregate has been very little explored, despite its practical applications. In this work we investigated the self-assembling properties of a PNA dimer, conjugated at the N-terminus to a fluorenylmethoxycarbonyl group. This PNA dimer forms nano-aggregates at low concentration in CHCl3 /CH3 OH mixtures. The aggregates retain very interesting fluorescent properties (high quantum yield in the visible region with lifetimes on the nanosecond scale), which make them promising materials for applications in optoelectronics.

Aggregation induced emission based “turn-off” fluorescent chemosensor for selective and swift sensing of mercury (II) ions in water

An Anthracene based fluorescent probe, 1-(Anthracen-2-yliminomethyl)-napthalen-2-ol (AIN), was synthesized via simple one-pot reaction from inexpensive reagents. Intriguingly, it exhibited novel AIE characteristics in H2O-THF mixtures at high water content. Size and growth process of particles in different volume percentage of water and THF mixtures were investigated using TRPL, DLS, SEM and optical microscope. The fluorescent aggregates exhibited distinct Hg2+-selective “on-off” type fluorescence switching upon binding. Additionally, the fluorescence quenching showed a linear correlation in the Hg2+ concentration range from 0.3 to 3.6 μM and the limit of detection was estimated as low as ∼3 ppb. The drastic decrease in emission intensity of AIN aggregates was observed in the presence of mercury ions via a complex interplay through the ground state complexation between AIN and Hg2+ ions and external heavy atom induced perturbation by Hg2+ ions to the excited states of the AIN. A large Stern–Volmer quenching constant was estimated to be 2.54 × 105 M−1. The proposed analytical system with clear AIE characteristics demonstrates a potential outlook for the on-site visual detection of Hg2+ in paper strips. Finally, the sensory probe was also applied to determine the concentration of Hg2+ in real water samples to demonstrate its practical applications.

A hydroxyquinoline-base nanoprobe for fluorescent sensing of Hg 2+ ion in aqueous solution

Abstract A new amphiphilic probe Q-16 bearing a hydroxylquinoline ring and a long hydrophobic cetyl chain has been synthesized and characterized. In aqueous solution, this probe can self-assemble fluorescent nano-structure aggregation, which is confirmed by the tyndall scattering experiment, dynamic light scattering (DLS) and transmission electron microscopy (TEM) techniques. Upon the addition of Hg 2+ , this probe shows a fluorescence quenching effect without interference from other metal ions. The detection limit of Q-16 to Hg 2+ is 4.42 nM. 1 H NMR titrations and DFT calculation results reveal that the triazole ring, the quinoline ring and the ether O atom of Q-16 play an important role for binding with the Hg 2+ center. However, probe Q-16 shows sensing of Hg 2+ , Cd 2+ , Ni 2+ , Cu 2+ and Al 3+ in CH 3 CN solution. Importantly, sensitivity and selectivity of Q-16 toward Hg 2+ in aqueous solution is higher than that in CH 3 CN solution for aggregation.

Glycosylated Cell‐Penetrating Poly(disulfide)s: Multifunctional Cellular Uptake at High Solubility

The glycosylation of cell‐penetrating poly(disulfide)s (CPDs) is introduced to increase the solubility of classical CPDs and to achieve multifunctional cellular uptake. With the recently developed sidechain engineering, CPDs decorated with α‐d‐glucose (Glu), β‐d‐galactose (Gal), d‐trehalose (Tre), and triethyleneglycol (TEG) were readily accessible. Confocal laser scanning microscopy images of HeLa Kyoto cells incubated with the new CPDs at 2.5 μm revealed efficient uptake into cytosol and nucleoli of all glycosylated CPDs, whereas the original CPDs and TEGylated CPDs showed much precipitation into fluorescent aggregates at these high concentrations. Flow cytometry analysis identified Glu‐CPDs as most active, closely followed by Gal‐CPDs and Tre‐CPDs, and all clearly more active than non‐glycosylated CPDs. In the MTT assay, all glyco‐CPDs were non‐toxic at concentrations as high as 2.5 μm. Consistent with thiol‐mediated uptake, glycosylated CPDs remained dependent on thiols on the cell surface for dynamic covalent exchange, their removal with Ellman's reagent DTNB efficiently inhibited uptake. Multifunctionality was demonstrated by inhibition of Glu‐CPDs with d‐glucose (IC50 ca. 20 mm). Insensitivity toward l‐glucose and d‐galactose and insensitivity of conventional CPDs toward d‐glucose supported that glucose‐mediated uptake of the multifunctional Glu‐CPDs involves selective recognition by glucose receptors at the cell surface. Weaker but significant sensitivity of Gal‐CPDs toward d‐galactose but not d‐glucose was noted (IC50 ca. 110 mm). Biotinylation of Glu‐CPDs resulted in the efficient delivery of streptavidin together with a fluorescent model substrate. Protein delivery with Glu‐CPDs was more efficient than with conventional CPDs and remained sensitive to DTNB and d‐glucose, i.e., multifunctional.

Real-Time Trafficking of Agrobacterium Virulence Protein VirE2 Inside Host Cells.

A. tumefaciens delivers T-DNA and virulence proteins, including VirE2, into host plant cells, where T-DNA is proposed to be protected by VirE2 molecules as a nucleoprotein complex (T-complex) and trafficked into the nucleus. VirE2 is a protein that can self-aggregate and contains targeting sequences so that it can efficiently move from outside of a cell to the nucleus. We adopted a split-GFP approach and generated a VirE2-GFP fusion which retains the self-aggregating property and the targeting sequences. The fusion protein is fully functional and can move inside cells in real time in a readily detectable format: fluorescent and unique filamentous aggregates. Upon delivery mediated by the bacterial type IV secretion system (T4SS), VirE2-GFP is internalized into the plant cells via clathrin adaptor complex AP2-mediated endocytosis. Subsequently, VirE2-GFP binds to membrane structures such as the endoplasmic reticulum (ER) and is trafficked within the cell. This enables us to observe the highly dynamic activities of the cell. If a compound, a gene, or a condition affects the cell, the cellular dynamics shown by the VirE2-GFP will be affected and thus readily observed by confocal microscopy. This represents an excellent model to study the delivery and trafficking of an exogenously produced and delivered protein inside a cell in a natural setting in real time. The model may be used to explore the theoretical and applied aspects of natural protein delivery and targeting.

AIE + ESIPT based red fluorescent aggregates for visualization of latent fingerprints

DPSA shows applications in establishing the individuality of three subjects using the 1st (pattern of arch, loop or whorl) and 2nd (minutiae details of dots, ridge ending, core and delta) level of information.

Lithium Ion Nanocarriers Self-Assembled from Amphiphiles with Aggregation-Induced Emission Activity

Lithium salts are extensively used to treat diseases such as bipolar disorder or chronic reduction, but they often trigger undesirable side effects in patients due to the accumulation of lithium ions in peripheral organs. A conventional strategy for fabricating nanocarriers is not applicable to lithium ions because of their difficulty in binding firmly to molecules in water and easy leakage due to their small size and high water solubility. We report here the successful fabrication of lithium ion nanocarriers in water with an amphiphile containing two ethylene oxide tetramers attached to a hydrophobic core showing aggregation-induced light emission (AIE). The amphiphile self-assembles into fluorescent spherical aggregates in water. Lithium ions are loaded into the spherical aggregates by binding to the ethylene oxide tetramer. This nanocarrier can enter cells facilely via an endocytosis process and does not affect the cell viability at concentrations of up to 100 μM. Moreover, the self-imaging ability of ...

Photophysics of Zinc Porphyrin Aggregates in Dilute Water-Ethanol Solutions.

Dimeric and multimeric aggregates of a model metalloporphyrin, zinc tetraphenylporphyrin (ZnTPP), have been produced in a controlled manner by incrementally increasing the water content of dilute aqueous ethanol solutions. Steady state absorption, fluorescence emission, and fluorescence excitation spectra have been measured to identify the aggregates present as a function of solvent composition. The dynamics of the excited states of the aggregates produced initially by excitation in the Soret region have been measured by ultrafast fluorescence upconversion techniques. Only the monomer produces measurable emission from S2 with a picosecond lifetime; all Soret-excited aggregates, including the dimer, decay radiationlessly on a femtosecond time scale. The S1 state is the only significant product of the radiationless decay of the S2 state of the excited monomer, and the aggregates also produce substantial quantum yields of S1 fluorescence when initially excited in the Soret region. The resulting fluorescent aggregates all decay on a subnanosecond time scale, likely by a mechanism that involves dissociation of the excited monomer from the excitonic multimer. The ZnTPP dimers excited at their ground state geometries in the Soret region exhibit a dynamic behavior that is quite different from those produced following noncoherent triplet-triplet annihilation under the same conditions. The important implications of these observations in determining the aggregation conditions promoting efficient photon upconversion by excitonic annihilation in a variety of media are thoroughly discussed.

AIEE Active Donor-Acceptor-Donor-Based Hexaphenylbenzene Probe for Recognition of Aliphatic and Aromatic Amines.

In the present investigation, an intramolecular charge transfer (ICT) and aggregation induced emission enhancement (AIEE) active donor-acceptor-donor (D-A-D) system 5 having fumaronitrile as the acceptor and hexaphenylbenzene (HPB) as the donor moieties joined through rotatable phenyl rings has been designed and synthesized that is highly emissive in the solid state and exhibits stimuli-responsive reversible piezochromic behavior upon grinding and heating. Because of its AIEE characteristics, HPB derivative 5 undergoes aggregation to form fluorescent aggregates in mixed aqueous media that exhibit ratiometric fluorescence response toward aliphatic amines (primary/secondary/tertiary) and turn-off response toward aromatic amines and hence differentiates between them. Further, the solution-coated portable paper strips of derivative 5 showed pronounced and sensitive response toward aromatic and aliphatic amines with a detection limit in the range of picogram and nanogram level, respectively.

Toxicity and infectivity: insights from de novo prion formation.

Prions are infectious misfolded proteins that assemble into oligomers and large aggregates, and are associated with neurodegeneration. It is believed that the oligomers contribute to cytotoxicity, although genetic and environmental factors have also been shown to have additional roles. The study of the yeast prion [PSI +] has provided valuable insights into how prions form and why they are toxic. Our recent work suggests that SDS-resistant oligomers arise and remodel early during the prion formation process, and lysates containing these newly formed oligomers are infectious. Previous work shows that toxicity is associated with prion formation and this toxicity is exacerbated by deletion of the VPS5 gene. Here, we show that newly made oligomer formation and infectivity of vps5∆ lysates are similar to wild-type strains. However using green fluorescent protein fusions, we observe that the assembly of fluorescent cytoplasmic aggregates during prion formation is different in vps5∆ strains. Instead of large immobile aggregates, vps5∆ strains have an additional population of small mobile foci. We speculate that changes in the cellular milieu in vps5∆ strains may reduce the cell's ability to efficiently recruit and sequester newly formed prion particles into central deposition sites, resulting in toxicity.

Grinding of Class-F fly ash using planetary ball mill: A simulation study to determine the breakage kinetics by direct- and back-calculation method

Dry grinding of Class F fly ash (FA) was carried out using the planetary ball mill to obtain mechanically activated nanostructured FA particles. The resulting FA powders were characterized for (i) particle size: dynamic light scattering and sieve analyzer, (ii) specific surface area: BET-analyzer, (iii) structure: X-ray diffractometer, (iv) chemical composition: field emission scanning electron microscope with the electron diffraction spectrum analyzer and x-ray fluorescence analyzer, and (v) aggregation and shape of the particles: Fourier-transformed infra-red spectrometer and scanning electron microscope. A significant enhancement in surface and bulk properties of milled FA was obtained over fresh FA. The breakage parameters (i.e., the specific rate of breakage and primary breakage distribution function) of FA were determined by the direct experimental method using the narrowly-sized fraction of FA over the short grinding period under identical milling environment. A relatively simple back-calculation method was employed to determine above breakage parameters of FA also using time-variant milling data that were obtained after the grinding of distributed-sized FA feed. The parameters obtained from the direct experimental and back-calculation method yielded comparative milling simulation results with the acceptable accuracy.

Fish TRIM35 negatively regulates the interferon signaling pathway in response to grouper nodavirus infection

Tripartite motif-containing protein 35 (TRIM35) has been demonstrated to exert critical roles in cancer, cell death and other multiple cell processes. However, the precisely roles of TRIM35 during virus infection still remained largely unknown. In the current study, we cloned a TRIM35 gene from orange spotted grouper (EcTRIM35) and uncovered its roles in response to nodavirus infection. EcTRIM35 encoded a 456-aa protein which showed 65% and 32% identity to large yellow croaker (Larimichthys crocea) and human (Homo sapiens), respectively. Structure prediction and amino acid alignment analysis indicated that EcTRIM35 contained three conserved domains, including RING domain, B-BOX and SPRY domain. In healthy grouper, the high expression level of EcTRIM35 could be detected in liver, spleen and intestine. After infection with red-spotted grouper nervous necrosis (RGNNV) and Singapore grouper iridovirus (SGIV) in GS cells, the transcript of EcTRIM35 was significantly up-regulated with the infection time increased. Under fluorescence microscopy, the bright fluorescence aggregates were observed in EcTRIM35 transfected cells, but the fluorescence distribution was obviously altered in the EcTRIM35-ΔRING transfected cells. After incubation with RGNNV, the overexpression of EcTRIM35 in vitro significantly enhanced the viral replication, evidenced by the enhancement of cytopathic effect (CPE) severity and the up-regulation of the viral gene transcription. Moreover, the ectopic expression of EcTRIM35 significantly decreased the expression of interferon signaling molecules or effectors. Further studies elucidated that EcTRIM35 overexpression significantly weakened the MAVS-, MITA- or TBK1-induced interferon immune response, but showed no effects on MDA5-induced immune response. Thus, our results will shed new lights on the roles of fish TRIM35 in innate immune response against grouper virus infection.

Hexaphenylbenzene appended AIEE active FRET based fluorescent probe for selective imaging of Hg2+ ions in MCF-7 cell lines

Hexaphenylbenzene (HPB) appended rhodamine derivative 4 has been synthesized which exhibits aggregation-induced emission enhancement (AIEE) characteristics and forms fluorescent aggregates in mixed aqueous media. These aggregates show remarkable fluorescence resonance energy transfer (FRET) in the presence of Hg2+ ions among various metal ions tested. Further these aggregates were also utilized for the ratiometric imaging of Hg2+ ions in MCF-7 cell lines.

Polythiophene-Encapsulated Bimetallic Au-Fe3O4Nano-Hybrid Materials: A Potential Tandem Photocatalytic System for Nondirected C(sp2)–H Activation for the Synthesis of Quinoline Carboxylates

Hetero-oligophenylene derivative 3 appended with thiophene moieties has been designed and synthesized which undergoes aggregation to form J-type fluorescent aggregates in in H2O/THF (7/3) media. These aggregates served as reactors for the preparation of bimetallic Au-Fe3O4 NPs. During the reduction process, aggregates of derivative 3 were oxidized to the polythiophene species 4. Interestingly, the polythiophene species 4, having a fibrous morphology, served as a shape- and morphology-directed template for assembly of bimetallic Au-Fe3O4 NPs in a flower-like arrangement. Furthermore, polythiophene-encapsulated bimetallic 4:Au-Fe3O4 nanohybrid materials served as an efficient and recyclable catalytic system for C(sp2)–H bond activation of unprotected electron-rich anilines for the construction of synthetically versatile quinoline carboxylates via C–H activation, carbonylation, and subsequent annulation under mild and eco-friendly conditions (aqueous media, room temperature, visible-light irradiation, and aerial conditions).

Solvatochromic and Fluorogenic Dyes as Environment-Sensitive Probes: Design and Biological Applications.

Fluorescent environment-sensitive probes are specially designed dyes that change their fluorescence intensity (fluorogenic dyes) or color (e.g., solvatochromic dyes) in response to change in their microenvironment polarity, viscosity, and molecular order. The studies of the past decade, including those of our group, have shown that these molecules become universal tools in fluorescence sensing and imaging. In fact, any biomolecular interaction or change in biomolecular organization results in modification of the local microenvironment, which can be directly monitored by these types of probes. In this Account, the main examples of environment-sensitive probes are summarized according to their design concepts. Solvatochromic dyes constitute a large class of environment-sensitive probes which change their color in response to polarity. Generally, they are push-pull dyes undergoing intramolecular charge transfer. Emission of their highly polarized excited state shifts to the red in more polar solvents. Excited-state intramolecular proton transfer is the second key concept to design efficient solvatochromic dyes, which respond to the microenvironment by changing relative intensity of the two emissive tautomeric forms. Due to their sensitivity to polarity and hydration, solvatochromic dyes have been successfully applied to biological membranes for studying lipid domains (rafts), apoptosis and endocytosis. As fluorescent labels, solvatochromic dyes can detect practically any type of biomolecular interactions, involving proteins, nucleic acids and biomembranes, because the binding event excludes local water molecules from the interaction site. On the other hand, fluorogenic probes usually exploit intramolecular rotation (conformation change) as a design concept, with molecular rotors being main representatives. These probes were particularly efficient for imaging viscosity and lipid order in biomembranes as well as to light up biomolecular targets, such as antibodies, aptamers and receptors. The emerging concepts to achieve fluorogenic response to the microenvironment include ground-state isomerization, aggregation-caused quenching, and aggregation-induced emission. The ground-state isomerization exploits, for instance, polarity-dependent spiro-lactone formation in silica-rhodamines. The aggregation-caused quenching uses disruption of the self-quenched dimers and nanoassemblies of dyes in less polar environments of lipid membranes and biomolecules. The aggregation-induced emission couples target recognition with formation of highly fluorescent dye aggregates. Overall, solvatochromic and fluorogenic probes enable background-free bioimaging in wash-free conditions as well as quantitative analysis when combined with advanced microscopy, such as fluorescence lifetime (FLIM) and ratiometric imaging. Further development of fluorescent environment-sensitive probes should address some remaining problems: (i) improving their optical properties, especially brightness, photostability, and far-red to near-infrared operating range; (ii) minimizing nonspecific interactions of the probes in biological systems; (iii) their adaptation for advanced microscopies, notably for superresolution and in vivo imaging.

Unusual cis-diprotonated forms and fluorescent aggregates of non-peripherally alkoxy-substituted metallophthalocyanines.

Protonation and aggregation of two metallophthalocyanines (zinc and magnesium) non-peripherally substituted with 1,4,7-trioxanonyl moieties were studied by steady-state and time-resolved optical spectroscopy. Both compounds are easily protonated in organic solvents, but the central metal ion strongly affects the character of this process. In particular, the magnesium derivative forms the cis-diprotonated isomer observed for the first time in phthalocyanines, in contrast to its zinc counterpart which forms the typical trans-diprotonated isomer. In addition, studies performed on phthalocyanines substituted with n-butoxy groups at their non-peripheral positions indicated that the formation of the cis-diprotonated forms is a more common feature of alkoxy-substituted magnesium metallophthalocyanines, in contrast to derivatives with other metal ions. The cis-diprotonated forms of the magnesium derivatives are formed at much lower proton concentrations than the trans-diprotonated forms of their zinc counterparts. The cis-isomers were also found to have more advantageous photophysical properties for photoactive applications than the trans-isomers. Aggregation studies of the trioxanonyl phthalocyanines revealed that the magnesium derivative aggregates much more easily in non-coordinating solvents than its zinc counterpart. Both the derivatives form fluorescent aggregates, which is typically attributed to the presence of oxygen-to-metal intermolecular coordination preventing the formation of non-fluorescent face-to-face stacks. The results indicate that the oxygen-to-metal coordination plays a significant role in the studied systems and the stronger oxygen-coordination ability of magnesium ions compared to zinc ions may underlie the observed differences between the phthalocyanines metallated with these two ions.

Pillararene-based fluorescent chemosensors: recent advances and perspectives.

In 2008, a new class of pillar-shaped supramolecular macrocyclic hosts was reported, known as "pillararenes". Their particular electron-rich cavity and the ease of their functionalization offer possibilities for the design and synthesis of novel fluorescent chemosensors. Subsequently, pillararene-based fluorescent sensors and probes have been rapidly developed. This feature article covers the most recent contributions from the pillararene-based fluorescent sensor field in terms of anion/cation sensing, small molecule recognition, biomolecule detection, fluorescent supramolecular aggregates, and biomedical imaging. Meanwhile, we hope that this feature article will inspire more effort to be devoted to this emerging field.

Hexaphenylbenzene-based fluorescent aggregates for detection of zinc and pyrophosphate ions in aqueous media: tunable self-assembly behaviour and construction of a logic device

The aggregates of HPB derivative 7 exhibited “on–on” response towards Zn2+ ions and this in situ prepared 7-Zn2+ ensemble was utilized as a “not quenched” probe for detection of PPi ions in aqueous media.