Tuning fluorescence colour of solid-state materials has become a topic of increasing interest for both fundamental mechanism study and practical applications such as sensors, optical recording and security printing. In this work, a fluorescent colour tuneable molecule BA-C16 is rationally designed and facilely synthesized by attaching flexible long alkyl chains to 2-hydroxybenzophenone azine (BA), which shows both aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. Compared to BA, the simple introduction of long alkyl chains in BA-C16 leads to an emission wavelength redshift from 542 to 558 nm. This strategy of extending emission wavelength is rarely reported, and is ascribed to the enlarged through-space π-conjugation between interplanar molecules in the aggregate of BA-C16. Three crystals of BA-C16 are obtained with green, yellowish green and yellow emission. According to characterization by X-ray crystallography, X-ray powder diffraction and differential scanning calorimetry, alkyl chains play an important role in inducing different stacking modes of the three crystals, which further leads to polymorph-dependent fluorescence colour. BA-C16 exhibits tuneable solid-state fluorescence upon vapor fumigation, or annealing based on a transition between a "near-monomer" crystalline state and a "dimer" crystalline state. BA-C16 is further applied for rewritable fluorescence printing tuned by vapor- and thermal-treatment.

Tuning fluorescence color of solid-state materials has great potential. Herein, a fluorescent color tunable molecule BA-C16 is rationally designed and facilely synthesized by attaching flexible long alkyl chains to an AIEgen 2-hydroxybenzophenone azine (BA), extending emission wavelength red-shift from 542 nm to 558 nm. This extending emission wavelength strategy is rarely reported and is ascribed to the enlarged through-space π-conjugation between interplanar molecules in the aggregate of BA-C16. More information can be found in the Full Paper by A. Tong et al. on page 8043.

A novel fluorescent probe DNBS-CSA is developed for light-up detection of β-lactamase. The probe design is based on an indirect detection approach with three step reactions. β-Lactamase can react with the lactam of its substrate (cefazolin sodium) to produce a secondary amine, initiating a spontaneous elimination reaction and affording a thiol compound. The thiol could further react with the sulfonate group of DNBS-CSA, releasing the salicylaldehyde azine derivative (CSA) with both aggregation induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. Previously reported β-lactamase probes require covalent linkage of the substrate β-lactam ring part to the probe, which makes probe synthesis difficult due to the complicated structure of the β-lactam ring. In contrast, modification of the β-lactam ring is no longer necessary for DNBS-CSA according to our indirect detection approach. The linear range of fluorescence quantification for β-lactamase is 0-10 mU mL-1 in an aqueous solution. Moreover, owing to the AIE properties of CSA, detection of β-lactamase with DNBS-CSA on test papers was also achieved.

A ratiometric fluorescence detection method for trace amount of uranyl ion (UO22+) was developed in this study, based on aggregation induced emission enhancement (AIEE) characteristics of 3-hydroxyflavone salicylaldehyde azine (HFSA) and luminescent signal of UO22+-HFSA complex in soluble state. The fluorescent ratio (I457/I534) was linearly related to the concentration of UO22+ in the range of 0.5–20 ppb (part per billion). Analytical data showed that a detection limit of 0.5 ppb was achieved with the relative standard deviation (R.S.D.) 1.3% (n=5). The proposed method could also be utilized for imaging UO22+ in living cells by ratiometric fluorescence changes.

The development of red fluorophores with efficient solid-state emission is still challenging. Herein, a red fluorophore 1 with aggregation-induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics is rationally designed and facilely synthesized by attaching an electron-donor diethylamine and an electron-acceptor maleonitrile group to salicyladazine. In contrast to many red fluorophores which undergo serious aggregation-caused quenching (ACQ), compound 1 emits bright red fluorescence (λem = 650 nm, ΦF = 24.3%) in the solid state with a large Stokes shift of 174 nm. Interestingly, control compounds 2 and 3, which have similar structures as 1, exhibit obvious aggregation-caused quenching (ACQ) characteristics. The difference in the crystal structures of 1, 2, and 3 reveals that the interplanar spacing among molecules plays a decisive role in realizing the AIE characteristics of 1. Moreover, when the hydroxyl group of 1 was substituted by an esterase reactive acetoxyl, a fluorescence light-up probe 4 was developed for sensing of esterase based on the selective reaction between 4 and esterase to generate the AIE and ESIPT active molecule 1. The linear range for in vitro quantification of esterase is 0.01-0.15 U/mL with a detection limit of 0.005 U/mL. Probe 4 was also successfully applied to image esterase in mitochondria of living cells.

Cells interact with the extracellular environment through molecules expressed on the membrane. Disruption of these membrane-bound interactions (or encounters) can result in disease progression. Advances in super-resolution microscopy have allowed membrane encounters to be examined, however, these methods cannot image entire membranes and cannot provide information on the dynamic interactions between membrane-bound molecules. Here, we show a novel DNA probe that can transduce transient membrane encounter events into readable cumulative fluorescence signals. The probe, which translocates from one anchor site to another, mimicking motor proteins, is realized through a toehold-mediated DNA strand displacement reaction. Using this probe, we successfully monitored rapid encounter events of membrane lipid domains using flow cytometry and fluorescence microscopy. Our results show a preference for encounters within the same lipid domains.

A ratiometric fluorescence detection method for trace amount of uranyl ion (UO22+) was developed in this study, based on aggregation induced emission enhancement (AIEE) characteristics of 3-hydroxyflavone salicylaldehyde azine (HFSA) and luminescent signal of UO22+-HFSA complex in soluble state. The fluorescent ratio (I457/I534) was linearly related to the concentration of UO22+ in the range of 0.5–20 ppb (part per billion). Analytical data showed that a detection limit of 0.5 ppb was achieved with the relative standard deviation (R.S.D.) 1.3% (n=5). The proposed method could also be utilized for imaging UO22+ in living cells by ratiometric fluorescence changes.

In this paper, mechanoresponsive fluorescent molecules with high “off–on” contrast ratios that undergo molecular packing transformation from amorphous phase to crystalline by scratching are first reported. Three 2-aminobenzophenone derivatives 1, 2, and 3, which possess crystallization-induced fluorescence characteristics, exhibited bright cyan, blue, and green fluorescence colors with “off–on” contrast ratios as high as 175-fold by scratching. The scratching induced transformation from amorphous phase to crystalline of 1, 2, and 3 were directly observed by XRD and SEM studies. In addition, the fluorescence of the scratched sample can readily convert back into the initial nonfluorescent state by fuming in ethanol or heating. Letters with three fluorescence emission colors of 1, 2, and 3 in ethanol solution smeared on a glass surface can be easily written by scratching and erased by fumigation, demonstrating the potential value as reversible mechanoresponsive fluorescent materials.

RNA viruses, particularly, the highly pathogenic avian influenza (HPAI) virus, pose serious health concerns, and cause huge economic losses worldwide. Diagnostic tools for the early detection of these deadly RNA viruses are urgently needed to implement treatment and disease control strategies. Conventional reverse transcription polymerase chain reaction (RT-PCR)-based chemiluminescent (RT-PCR-CL) detection is frequently used for the diagnosis of viral infections. However, the requirements for expensive PCR machines and longer thermocycling times are significant drawbacks. In this study, we propose a method based on reverse transcription loop-mediated isothermal amplification (RT-LAMP) combined with chemiluminescence (CL) to detect H7N9 virus. The proposed method does not require any expensive instruments, and processing time is remarkably shortened compared to that of RT-PCR-CL. Since several factors including RT-LAMP temperature, probe concentration, hybridization temperature, and hybridization duration might affect the CL signal, each of these parameters was investigated and optimized. One thousand copies/mL of H7N9 RNA were detectable using the optimized RT-LAMP-CL method. The detection time was significantly reduced by using RT-LAMP, in comparison with conventional RT-PCR-CL. This technique holds great promise for viral detection and diagnosis, especially with regard to avian influenza virus.

A novel fluorescent probe SA-βGal is reported here with light-up response to β-galactosidase. SA-βGal possesses the β-galactopyranoside group to react with β-galactosidase and releases the fluorescent salicylaldehyde azine with both aggregation induced emission (AIE) and excited-state intramolecular proton transfer (ESIPT) characteristics. The linear fluorescent response enables the in vitro quantification of β-galactosidase activity in a range of 0-0.1 U mL-1 with a detection limit of 0.014 U mL-1. The probe exhibits significant advantages, such as no self-quenching at high concentrations, a large Stokes shift (190 nm) and high specificity to β-galactosidase with an excellent light-up ratio of 820 fold. Moreover, thanks to its good retention in living cells, the application of SA-βGal for the imaging of cellular β-galactosidase was also achieved with high contrast.

Photoactivatable (caged) fluorophores are widely used in chemistry, materials, and biology. However, the development of such molecules exhibiting photoactivable solid-state fluorescence is still challenging due to the aggregation-caused quenching (ACQ) effect of most fluorophores in their aggregate or solid states. In this work, we developed caged salicylaldehyde hydrazone derivatives, which are of aggregation-induced emission (AIE) characteristics upon light irradiation, as efficient photoactivatable solid-state fluorophores. These compounds displayed multiple-color emissions and ratiometric (photochromic) fluorescence switches upon wavelength-selective photoactivation, and were successfully applied for photopatterning and photoactivatable cell imaging in a multiple-color and stepwise manner.

Conventional fluorophores usually undergo aggregation-caused quenching (ACQ), which limits the loading amount of these fluorophores in nanoparticles for bright fluorescence imaging. On the contrary, fluorophores with aggregation-induced emission (AIE) characteristics are strongly fluorescent in their aggregate states and have been an ideal platform for developing highly fluorescent nanomaterials, such as fluorescent silica nanoparticles (FSNPs). In this work, AIE luminogens based on salicylaldehyde hydrazones were embedded in silica nanoparticles through a facile noncovalent approach, which afforded AIE-FSNPs emitting much brighter fluorescence than that of some commercial fluorescein-doped silica and polystyrene nanoparticles. These AIE-FSNPs displaying multiple fluorescence colors were fabricated by a general method, and they underwent much less fluorescence variation due to environmental pH changes compared with fluorescein-hybridized FSNPs. In addition, a DNA aptamer specific to nucleolin was functionalized on the surface of AIE-FSNPs for targeted cell imaging. Fluorescent microscopy and flow cytometry studies both revealed highly selective fluorescence staining of MCF-7 (a cancer cell line with nucleolin overexpression) over MCF-10A (normal) cells by the aptamer-functionalized AIE-FSNPs. The fluorescence imaging in different color channels was achieved using AIE-FSNPs containing each of the AIE luminogens, as well as photoactivatable fluorescent imaging of target cells by the caged AIE fluorophore.

A new method for caspase 3 activity assay has been developed based on HRP-mimicking DNAzyme-peptide conjugates. The mechanism of detection was based on the specific cleavage of DEVD-peptides by active caspase 3 for recognition and the catalytic properties of HRP-mimicking DNAzymes for signal amplification. Under optimal conditions, the detection limit of caspase 3 was 0.89 nM. The proposed method was also successfully applied for the detection of caspase 3 in apoptosis cell lysates.

An azobenzene-containing surfactant was synthesized for the phase transfer of α-cyclodextrin (α-CD)-capped gold nanoparticles between water and toluene phases by host–guest chemistry. With the use of the photoisomerization of azobenzene, the reversible phase transfer of gold nanoparticles was realized by irradiation with UV and visible light. Furthermore, the phase transfer scheme was applied for the quenching of a reaction catalyzed by gold nanoparticles, as well as the recovery and recycling of the gold nanoparticles from aqueous solutions. This work will have significant impact on materials transfer and recovery in catalysis and biotechnological applications.

A ratiometric fluorescent chemosensor 1 was developed for the detection of Al3+ in aqueous solution based on aggregation-induced emmision (AIE). The chemosensor showed the fluorescence of its aggregated state and Al3+-chelated soluble state in the absence and in the presence of Al3+, respectively, and resulted in a fluorescence ratio (I461/ I537) response to Al3+ in neutral aqueous solution at a detection limit as low as 0.29 mu mol L (1). The method was also highly selective to Al3+ over other physiological relevant metal ions investigated in this study. Taking advantage of its AIE characteristics, the chemosensor was successfully applied on test papers for simple and rapid detection of Al3+. Moreover, the application of 1 for the imaging of Al3+ in living cells by ratiometric fluorescence changes was also achieved. (C) 2014 Elsevier B.V. All rights reserved.

Cell types, both healthy and diseased, can be classified by inventories of their cell-surface markers. Programmable analysis of multiple markers would enable clinicians to develop a comprehensive disease profile, leading to more accurate diagnosis and intervention. As a first step to accomplish this, we have designed a DNA-based device, called "Nano-Claw". Combining the special structure-switching properties of DNA aptamers with toehold-mediated strand displacement reactions, this claw is capable of performing autonomous logic-based analysis of multiple cancer cell-surface markers and, in response, producing a diagnostic signal and/or targeted photodynamic therapy. We anticipate that this design can be widely applied in facilitating basic biomedical research, accurate disease diagnosis, and effective therapy.

The emergence of hybrid materials combining biomacromolecules and organic polymers has received broad attention based on their potential applications in chemical, biological and materials sciences. Among different coupling strategies, the grafting of oligonucleotides to organic polymers as side chains by covalent bonds provides a novel platform whereby the properties of both oligonucleotides and polymer backbone are integrated, manipulated and optimized for various applications. In this review, we give the perspective on this specific type of DNA polymer hybrid materials , using selected examples with emphasis on bioanalysis, biomedicine and stimuli-responsive materials. It is expected the success of DNA-grafting polymers will not only impact the frabication of novel bimolecule incorporated materials, but also will influence how the properties of synthetic materials are tailored using different functional groups.

A novel fluorescent probe 1 is reported here with ratiometric response to hydrophobic proteins (casein) or proteins with hydrophobic pockets (BSA, HSA) through hydrophobic interaction. Probe 1 underwent deprotonation in aqueous solution at pH 7.4 and emitted blue fluorescence at 436 nm. Upon the addition of BSA, HSA or casein, the aggregation-induced emission fluorescence of 1 at 518 nm was turned on. The fluorescence intensity ratio, I518/I436 was linearly related to the concentrations of these proteins. The detection limits for BSA, HSA and casein based on IUPAC (CDL = 3Sb m(-1)) were 16.2 μg mL(-1), 10.5 μg mL(-1) and 5.7 μg mL(-1), respectively.

A simple and universal route for the preparation of metal-graphene oxide (GO) heterostructures with controllable nanoparticle size and shape using double-stranded DNA (dsDNA) as a template is reported. This proof-of-concept work successfully demonstrates that dsDNA can be adsorbed onto GO to create biocompatible and easily functionalizable Ag-GO, Au-GO, Cu-GO, Pt-GO, and Au/Cu/Pt-GO heterostructures using the same experimental conditions for each of the multicomposite nanoparticles.

Simultaneous monitoring of the expression, distribution, and dynamics of biological molecules in living cells is one of the most challenging tasks in the analytical sciences. The key to effective and successful intracellular imaging is the development of delivery platforms with high efficiency and ultrasensitive molecular probes for specific targets of interest. To achieve these goals, many nanomaterials are widely used as carriers to introduce nucleic acid probes into living cells for real-time imaging of biomolecules. However, limitations on their use include issues of cytotoxicity and delivery efficiency. Herein, we propose a switchable aptamer micelle flare (SAMF), formed by self-assembly of an aptamer switch probe-diacyllipid chimera, to monitor ATP molecules inside living cells. Similarity of hydrophobic composition between diacyllipids in the micelle flares and phospholipid bilayers in the dynamic membranes of living cells allows SAMFs to be uptaken by living cells more efficiently than aptamer switch probes without external auxiliary. Switchable aptamers were found to bind target ATP molecules with high selectivity and specificity, resulting in restoration of the fluorescence signal from "OFF" to "ON" state, thus indicating the presence of the analyte. These switchable aptamer micelle flares, which exhibit cell permeability and nanoscale controllability, show exceptional promise for molecular imaging in bioanalysis, disease diagnosis, and drug delivery.