Fluorescent Organic Molecules Research Articles

Tracking lithium ions in an electrolyte

Over time, lithium-ion batteries need more frequent recharging. And on rare occasions, the batteries can catch fire when lithium builds up on the anode, forming sharp spikes that pierce the membrane that separates the anode from the cathode. A new way to directly image lithium ions could help researchers better understand why these problems happen (ACS Sens. 2017, DOI: 10.1021/acssensors.7b00087). Randall H. Goldsmith of the University of Wisconsin, Madison, and colleagues redesigned a fluorescent organic molecule that binds selectively to lithium ions so that the molecule fluoresces when excited by blue light instead of ultraviolet light, which can reduce image quality. The researchers then created a simple test platform consisting of the molecule—2-(2-hydroxyphenyl)naphthoxazole (shown)—and an electrolyte within a microfluidic channel. They injected lithium chloride solutions into the channel and showed that the fluorescence intensity grew with increasing ion concentration. Then the group used the syste...

Ag@Aggregation-induced emission dye core/shell nanostructures with enhanced one- and two-photon fluorescence

Combining plasmonic nanostructures with two-photon fluorescence materials is a promising way to significantly enhance two-photon fluorescence. Ag@1,4-bis(2-cyano-2-phenylethenyl) benzene (BCPEB) core/shell nanostructures were fabricated by simply incubating the isolated Ag nanoparticles with BCPEB microrods in ethanol. BCPEB was chosen as the fluorescent organic molecule owing to the aggregation-induced-emission (AIE) nature which would reduce the emission loss as being practically applied in solid phase. By utilizing the match of the extinction spectrum of Ag nanoparticles and BCPEB's absorption band, the target Ag@BCPEB core/shell nanostructures showed an enhanced one-photon (12×) fluorescence, integrating with SERS signal as well. Moreover, the resultant second harmonic generation of Ag nanoparticles under two-photon excitation also well matched with the absorption band of BCPEB, and significant enhanced two-photon (17×) fluorescence was obtained. The confocal images of NIH-3T3 cells with these nanostructures under one- and two-photon excitation showed good contrast and brightness for bio-imaging.

Microwave formation and photoluminescence mechanisms of multi-states nitrogen doped carbon dots

In recent years, carbon dots (CDs) have attracted much attention in the material field because of their remarkable performance in various aspects. Therefore, the exploration of complex and variable photoluminescence mechanisms shows great significance. Herein, we present a systematic study on the correlation between the formation process and photoluminescence mechanisms through the characterization and analysis of three states of nitrogen doped carbon dots (N-CDs) obtained by microwave irradiation. At low temperature of 160°C, the small organic molecule polymer nanodots whose photoluminescence center is molecule state are obtained with superior quantum yield of about 51.61%. Increasing the reaction temperature up to 200°C, the intermediate transition products named carbon nanodots begin to appear. Prolonging the holding time, the typical carbon quantum dots with a special stable optical properties are finally generated, and their most photoluminescence arises from the carbon cores which are gained through the polymerization, dehydration, carbonation of organic fluorescent molecules. Furthermore, N-CDs have been applied in metal ions detection as well as animal and plant cell fluorescence imaging owing to their excellent water solubility and low cytotoxicity. Our exploration provides the theoretical basis for synthesis of CDs with different properties and purposes. In the near future, more high-quality CDs will be developed in order to better benefit the various fields of mankind.

Facile synthesis of polymeric fluorescent organic nanoparticles based on the self-polymerization of dopamine for biological imaging

Polymeric fluorescent organic nanoparticles (polymer-FONs) have raised considerable research attention for biomedical applications owing to their advantages as compared with fluorescent inorganic nanoparticles and small organic molecules. In this study, we presented an efficient, facile and environment-friendly strategy to produce polymer-FONs, which relied on the self-polymerization of dopamine and polyethyleneimine (PEI) in rather mild conditions. To obtain the final polymer-FONs, aldehyde group-containing copolymers (named as poly(UA-co-PEGMA)) were synthesized by reversible addition–fragmentation chain-transfer polymerization using polyethylene glycol methyl ether methacrylate (PEGMA) and 1-undecen-10-al (UA) as monomers. The dopamine was conjugated onto poly(UA-co-PEGMA) through a multicomponent reaction between UA and dopamine to obtain poly(UA-co-PEGMA)-DA, which was further utilized for preparation of polymer-FONs through self-polymerization of dopamine and PEI. 1H nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy and fluorescence spectroscopy were employed to characterize the structure, morphology, compositions and optical properties of these polymer-FONs. Cell viability and cell uptake behavior results suggested that these polymer-FONs possess good biocompatibility and can be potentially utilized for biomedical applications. More importantly, the method can be also applied to fabricate many other multifunctional polymer-FONs with great potential for biomedical applications.

Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules

AbstractInvited for the cover of this issue is the group of Bert M. Weckhuysen at Utrecht University. The image depicts the probe molecule‐based staining method applied to large zeolite crystals, and is drawn with inspiration from the well‐known surrealist artist Salvador Dalí. Read the full text of the article at 10.1002/chem.201700078.

Probing Zeolite Crystal Architecture and Structural Imperfections using Differently Sized Fluorescent Organic Probe Molecules.

A micro‐spectroscopic method has been developed to probe the accessibility of zeolite crystals using a series of fluorescent 4‐(4‐diethylaminostyryl)‐1‐methylpyridinium iodide (DAMPI) probes of increasing molecular size. Staining large zeolite crystals with MFI (ZSM‐5) topology and subsequent mapping of the resulting fluorescence using confocal fluorescence microscopy reveal differences in structural integrity: the 90° intergrowth sections of MFI crystals are prone to develop structural imperfections, which act as entrance routes for the probes into the zeolite crystal. Polarization‐dependent measurements provide evidence for the probe molecule's alignment within the MFI zeolite pore system. The developed method was extended to BEA (Beta) crystals, showing that the previously observed hourglass pattern is a general feature of BEA crystals with this morphology. Furthermore, the probes can accurately identify at which crystal faces of BEA straight or sinusoidal pores open to the surface. The results show this method can spatially resolve the architecture‐dependent internal pore structure of microporous materials, which is difficult to assess using other characterization techniques such as X‐ray diffraction.

Ultrabright fluorescent silica particles with a large number of complex spectra excited with a single wavelength for multiplex applications

We report on a novel approach to synthesize ultrabright fluorescent silica particles capable of producing a large number of complex spectra. The spectra can be excited using a single wavelength which is paramount in quantitative fluorescence imaging, flow cytometry and sensing applications. The approach employs the physical encapsulation of organic fluorescent molecules inside a nanoporous silica matrix with no dye leakage. As was recently demonstrated, such an encapsulation allowed for the encapsulation of very high concentrations of organic dyes without quenching their fluorescent efficiency. As a result, dye molecules are distanced within ∼5 nm from each other; it theoretically allows for efficient exchange of excitation energy via Förster resonance energy transfer (FRET). Here we present the first experimental demonstration of the encapsulation of fluorescent dyes in the FRET sequence. Attaining a FRET sequence of up to five different dyes is presented. The number of distinguishable spectra can be further increased by using different relative concentrations of encapsulated dyes. Combining these approaches allows for creating a large number of ultrabright fluorescent particles with substantially different fluorescence spectra. We also demonstrate the utilization of these particles for potential multiplexing applications. Though fluorescence spectra of the obtained multiplex probes are typically overlapping, they can be distinguished by using standard linear decomposition algorithms.

Highly Sensitive Detection of Organic Molecules on the Basis of a Poly(N-isopropylacrylamide) Microassembly Formed by Plasmonic Optical Trapping.

We demonstrate that a poly(N-isopropylacrylamide) (PNIPAM) microassembly, formed by plasmonic optical trapping, can provide the platform for a highly sensitive detection technique for fluorescent and nonfluorescent organic molecules dissolved in aqueous solution. PNIPAM microassemblies can be easily formed by a combination with a photothermal effect and an enhanced optical force. These physical phenomena were obtained through resonant excitation of localized surface plasmon (LSP). Sparsely distributed fluorescent or nonfluorescent molecules dissolved in solution can be extracted into the PNIPAM assembly, resulting in an increase in fluorescence or Raman signals. In particular, we successfully detected quite small amounts of analytes (rhodamine B) at the 10-9 mol/L level. Using LSP is an alternative approach in analytical chemistry and can be used in addition to surface enhanced Raman scattering and surface enhanced fluorescence.

Clay–Organic Hybrid Films Exhibiting Reversible Fluorescent Color Switching Induced by Swelling and Drying of a Clay Mineral

The interlayer space of clays is an interesting microenvironment to control the properties of included organic materials. In this study, chromic hybrid films consisting of synthetic saponite (SSA) and fluorescent organic molecules with planar π-conjugated systems were fabricated. The hybrid films exhibited reversible fluorescence color switching induced by swelling and drying, which caused the gallery height of SSA to change. Ultraviolet–visible absorption, steady-state and time-resolved fluorescence measurements of the hybrid films strongly suggested that the organic molecules formed an excimer in the swollen interlayer space of SSA, while they were a monomer in the dried interlayer space. The different emission wavelengths of the excimer and monomer resulted in the fluorescence color switching of the hybrid films. The reversibility of the color switching was maintained for at least 50 cycles with no change of fluorescence maxima. These chromic hybrid films represent a novel approach to obtain color swit...

A Novel Mechanism for Chemical Sensing Based on Solvent–Fluorophore–Substrate Interaction: Highly Selective Alcohol and Water Sensor with Large Fluorescence Signal Contrast

Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.

AIEgens-Functionalized Inorganic-Organic Hybrid Materials: Fabrications and Applications.

Inorganic materials functionalized with organic fluorescent molecules combine advantages of them both, showing potential applications in biomedicine, chemosensors, light-emitting, and so on. However, when more traditional organic dyes are doped into the inorganic materials, the emission of resulting hybrid materials may be quenched, which is not conducive to the efficiency and sensitivity of detection. In contrast to the aggregation-caused quenching (ACQ) system, the aggregation-induced emission luminogens (AIEgens) with high solid quantum efficiency, offer new potential for developing highly efficient inorganic-organic hybrid luminescent materials. So far, many AIEgens have been incorporated into inorganic materials through either physical doping caused by aggregation induced emission (AIE) or chemical bonding (e.g., covalent bonding, ionic bonding, and coordination bonding) caused by bonding induced emission (BIE) strategy. The hybrid materials exhibit excellent photoactive properties due to the intramolecular motion of AIEgens is restricted by inorganic matrix. Recent advances in the fabrication of AIEgens-functionalized inorganic-organic hybrid materials and their applications in biomedicine, chemical sensing, and solid-state light emitting are presented.

Rapid Imaging of Latent Fingerprints Using Biocompatible Fluorescent Silica Nanoparticles.

Fluorescent silica nanoparticles (FSNPs) are synthesized through the Stöber method by incorporating silane-modified organic dye molecules. The modified fluorescent organic dye molecule is able to be prepared by allylation and hydrosilylation reactions. The optical properties of as-prepared FSNPs are shown the similar optical properties of PR254A (allylated Pigment Red 254) and have outstanding photostability. The polyvinylpyrrolidone (PVP) is introduced onto the surface of FSNP to enhance the binding affinity of PVP-coated FSNP for latent fingerprints (LFPs) detection. The simple preparation and easy control of surface properties of FSNPs show potential as a fluorescent labeling material for enhanced latent fingerprint detection on hydrophilic and hydrophobic substrates in forensic science for individual identification.

Long range energy transfer in graphene hybrid structures

In this work we quantify the distance dependence for the extraction of energy from excited chromophores by a single layer graphene flake over a large separation range. To this end hybrid structures were prepared, consisting of a thin (2 nm) layer of a polymer matrix doped with a well chosen strongly fluorescent organic molecule, followed by an un-doped spacer layer of well-defined thicknesses made of the same polymer material and an underlying single layer of pristine, undoped graphene. The coupling strength is assessed through the variation of the fluorescence decay kinetics as a function of distance between the graphene and the excited chromophore molecules. Non-radiative energy transfer to the graphene was observed at distances of up to 60 nm; a range much greater than typical energy transfer distances observed in molecular systems.

Ultrasensitive molecular sensor using N-doped graphene through enhanced Raman scattering.

As a novel and efficient surface analysis technique, graphene-enhanced Raman scattering (GERS) has attracted increasing research attention in recent years. In particular, chemically doped graphene exhibits improved GERS effects when compared with pristine graphene for certain dyes, and it can be used to efficiently detect trace amounts of molecules. However, the GERS mechanism remains an open question. We present a comprehensive study on the GERS effect of pristine graphene and nitrogen-doped graphene. By controlling nitrogen doping, the Fermi level (E F) of graphene shifts, and if this shift aligns with the lowest unoccupied molecular orbital (LUMO) of a molecule, charge transfer is enhanced, thus significantly amplifying the molecule's vibrational Raman modes. We confirmed these findings using different organic fluorescent molecules: rhodamine B, crystal violet, and methylene blue. The Raman signals from these dye molecules can be detected even for concentrations as low as 10(-11) M, thus providing outstanding molecular sensing capabilities. To explain our results, these nitrogen-doped graphene-molecule systems were modeled using dispersion-corrected density functional theory. Furthermore, we demonstrated that it is possible to determine the gaps between the highest occupied and the lowest unoccupied molecular orbitals (HOMO-LUMO) of different molecules when different laser excitations are used. Our simulated Raman spectra of the molecules also suggest that the measured Raman shifts come from the dyes that have an extra electron. This work demonstrates that nitrogen-doped graphene has enormous potential as a substrate when detecting low concentrations of molecules and could also allow for an effective identification of their HOMO-LUMO gaps.

A novel sensitive and selective nanocomposite sensor for Doxorubicin based on Graphene Oxide and fluorescent [2]Rotaxane

Graphene oxide (GO) displays advantageous characteristics as a quencher due to its excellent quenching capacity toward organic fluorescent molecules. In this paper, GO is used as a quencher of RhBPy [2]rotaxane based on the mechanism of fluorescence resonance energy transfer (FRET), and a GO-based fluorescent probe that allows rapid, sensitive and selective detection of doxorubicin (DOX) in a MeOH/H2O solution is reported. The results show that the efficient fluorescence quenching that occurs between GO and RhBPy [2]rotaxane is due to their strong noncovalent interactions via energy transfer, leading to very weak emission in the absence of DOX, while a strong red fluorescence is observed upon the addition of DOX into the RhBPy-GO solution. As a consequence, it is possible to employ the RhBPy-GO platform in DOX detection with high sensitivity and selectivity by monitoring changes in the fluorescence intensity of the MeOH/H2O (3:2, v: v) solution.

Measurement of lifetimes of triplet states of organic molecules by fluorescence recovery kinetics

The possibility of measuring the lifetime of triplet states of fluorescent complex organic molecules by fluorescence recovery kinetics after switching off the excitation source under saturation conditions is shown using the example of protoporphyrin IX.

Synthesis and Properties of New Imidazole-Based Organic Fluorescent Small Molecule

A series of phenothiazine (or triphenylamine)-substituted imidazoles were designed and synthesized as new organic fluorescent molecules by multi-step reactions. The relationship of their photoluminescence properties and structure was inves- tigated via UV-Vis, fluorescence and electrochemical analyzer. Their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) distributions were calculated by density functional theory (DFT) (B3LYP; 6-31G*) calculations. The high fluorescence quantum yields, desirable HOMO levels and high thermal stabilities of products indicated that the combination of imidazole and phenothiazines or triphenylamine is an efficient way to enhance hole transporting ability and fluorescent quantum yield.

Fabrication of Fluorescent Nanowires via High-Energy Particles-Triggered Polymerization Reactions

Highly fluorescent nanowires were produced quantitatively by one-for-one reactions between a high energy charged particle and fluorescent organic molecules via efficient solid-state polymerization reactions. The initiation and propagation reactions take place non-homogeneously along the trajectories of the particles within nm-sized cylindrical area, thus giving uniform nanowires with controlled sizes after isolation by removing non-irradiated (unreacted) molecules by organic solvents. Highly emissive properties of the nanowires even after isolation were clearly observed similar to their initial films, indicating that the polymerization process might not spoil the efficient fluorescent framework of the compound: excited state intra-molecular proton transfer (ESIPT) process. We also demonstrated that the fluorescent nanowires have potential of sensing the trace amount of nitrobenzene that was monitored by fluorescence spectroscopy.

Multifunctional optical sensing probes based on organic-inorganic hybrid composites.

Several hybrid sensing materials, which are prepared by the covalent grafting of organic fluorescent molecules onto inorganic supports, have emerged as a novel and promising class of hybrid sensing probes and have attracted tremendous interest. In comparison to the organic fluorescent sensors, the hybrid sensing probes incorporate the beneficial chemical/physical properties of the organic molecules and inorganic materials, which accelerate the development of hybrid materials for ion recognition and removal. Hence, the novel hybrid sensing materials can selectively monitor and efficiently remove specific analytes, which can provide a novel opportunity to synthesize multifunctional hybrid materials. Considerable efforts have been devoted to developing effective and innovative approaches for the design and synthesis of hybrid sensing materials that can display highly desirable performance for ion detection and removal. This tutorial review firstly presents a brief description of the hybrid materials and mesoporous silica materials and then classifies the hybrid sensing materials into several categories, including mesoporous silica based hybrid sensors, magnetic core-shell particle based hybrid sensors, magnetic nanoparticle based hybrid sensors, polymer based hybrid sensors, surface-grafted composite based hybrid sensors, and host-guest interaction based hybrid sensors, followed by a detailed summary of the design and synthesis of hybrid sensing materials and their applications in environmental and biological fields. Hopefully, this review will provide perspectives and guidelines for the development and further research of hybrid sensing materials.

An emission-tunable fluorescent organic molecule for specific cellular imaging

A color-tunable fluorescent molecule was synthesized and applied in specific lysosomal imaging.