Colorimetric detection and removal of radioactive Co ions using sodium alginate-based composite beads.

We demonstrate a simple method for the visual determination and removal of Co ions using a bead-shaped, capturing probe based on hybridized sodium alginate. For Co ions, the designed protocol consisted of three main constituents: an azopyridine-based Co ion-probe for visual detection; sodium alginate as an adsorbent for the Co ion and a bead construct for removal and structure; silica as a linker for the probe and the alginate, leading to a robust structure. When the composite beads were exposed to Co ions, the yellow color of the beads turned to intensive violet and the color intensity was associated with the Co ion concentration. The color variation was quantified using red-green-blue (RGB) color values that were obtained with a scanner and evaluated with Photoshop. The technique achieved both visual recognition with obvious color change of the beads and efficient removal of the radioactive 60Co ion. The sensing and removal of any radioactive isotope could be achieved with an appropriate sensing probe, to provide a simple and universal platform for remediation.

Photoswitchable Emission Color Change in Nanodots Containing Conjugated Polymer and Photochrome.

A simple approach for the preparation of conjugated polymer (CP)-based fluorescent nanodots containing photochrome (dithienylethene, DTE) is reported. The CP in the nanodots was designed to exhibit dual emissions of blue and green. The photochromic, fluorescent, composite nanodots (PNDs) were able to tune the emission color from green to blue using selective energy transfer from the CP to DTE under ultraviolet (UV) irradiation. The UV-irradiation-induced ring closure of the DTE within the PNDs provided a spectral overlap between the green emission of the CP and the absorption of DTE, leading to quenching of the green emission and, concomitantly, maintaining of the blue emission. The photoswitchable fluorescent PNDs with high on-off green fluorescence contrast were successfully applied in a living zebrafish imaging. Our design strategy provided a versatile tool for constructing a special photomodulated color-changeable nanostructure in bioimaging.

Functionalized, Fluorescent, Conjugated Polymer Nanospheres for Protein Targeting via Förster Resonance Energy Transfer.

We report the preparation of fluorescent nanospheres based on conjugated polymers, which enables a facile fluorescence color tuning. The fluorescent nanospheres have aldehyde groups on the surface that enable the introduction of a protein ligand, biotin. The intrinsic fluorescence of the nanospheres allows detection of a dye-labeled target protein, streptavidin, via Förster resonance energy transfer. The controlled biofunctionalization of conjugated polymer-based fluorescent nanospheres represents a novel approach with high applicability to sensing of biological molecules.

Simultaneous detection and removal of radioisotopes with modified alginate beads containing an azo-based probe using RGB coordinates.

We prepared alginate beads that were modified with an azo-based probe molecule to monitor simultaneously the removal (by alginate) and probing (by the azo-probe molecule) of radioisotopes such as cobalt, strontium, and cesium ions. As an azo-probe molecule, Basic Orange 2 (BO2) was immobilized to the alginate bead. The BO2 in aqueous solution exhibited a slight red shift in absorption with a change in color from orange to dark orange upon addition of cobalt and strontium ions. In contrast, the color of BO2 did not change upon exposure to cesium ions. Thus, the covalently embedded BO2 in alginate beads could adsorb cobalt and strontium ions resulting in recognizable color change of the beads, which was induced by the formation of a complex between BO2 and metal ions. The color changes of the beads in the presence of metal ions were determined quantitatively using RGB color coordinate values. In addition to effectively removing metal ions, the colorimetric coordinate method provides a convenient and simple sensing technique for naked-eye metal ion detection.

Conjugated polymer dots-on-electrospun fibers as a fluorescent nanofibrous sensor for nerve gas stimulant.

A novel chemical warfare agent sensor based on conjugated polymer dots (CPdots) immobilized on the surface of poly(vinyl alcohol) (PVA)-silica nanofibers was prepared with a dots-on-fibers (DoF) hybrid nanostructure via simple electrospinning and subsequent immobilization processes. We synthesized a polyquinoxaline (PQ)-based CP as a highly emissive sensing probe and employed PVA-silica as a host polymer for the elctrospun fibers. It was demonstrated that the CPdots and amine-functionalized electrospun PVA-silica nanofibers interacted via an electrostatic interaction, which was stable under prolonged mechanical force. Because the CPdots were located on the surface of the nanofibers, the highly emissive properties of the CPdots could be maintained and even enhanced, leading to a sensitive turn-off detection protocol for chemical warfare agents. The prepared fluorescent DoF hybrid was quenched in the presence of a chemical warfare agent simulant, due to the electron transfer between the quinoxaline group in the polymer and the organophosphorous simulant. The detection time was almost instantaneous, and a very low limit of detection was observed (∼1.25 × 10(-6) M) with selectivity over other organophosphorous compounds. The DoF hybrid nanomaterial can be developed as a rapid, practical, portable, and stable chemical warfare agent-detecting system and, moreover, can find further applications in other sensing systems simply by changing the probe dots immobilized on the surface of nanofibers.

The detection of thrombin using a mixture of a fluorescent conjugated polyelectrolyte and fibrinogen and implementation of a logic gate.

A highly sensitive and selective detection of thrombin is accomplished using an emission color-tunable conjugated polyelectrolyte. The implementation of a combined logic gate is realized upon emission modulation of the system including the polymer, fibrinogen, thrombin, and heparin.

Aggregation-deaggregation-triggered, tunable fluorescence of an assay ensemble composed of anionic conjugated polymer and polypeptides by enzymatic catalysis of trypsin.

We prepared a water-soluble conjugated polymer composed of electron-donating units and electron-accepting groups in the backbone. The polymer exhibits a short wavelength (blue) emission in aqueous solution and long wavelength (red) emission in the solid state, because of intermolecular energy transfer. Considering this, we develop a new approach for the sensitive detection of trypsin, which is known to control pancreatic exocrine function, using an ensemble system composed of the anionically charged conjugated polymer and cationically charged polypeptides (such as polylysine and polyarginine). The blue-emitting, water-soluble conjugated polymer becomes aggregated upon exposure to the polypeptides, leading to a red-emitting assay ensemble. The red-emitting assay ensemble becomes dissociated in the conjugated polymer and polypeptide fragments by selective degradation of trypsin, which then exhibits recovery of blue emission. This emission-tuning assay ensemble allows for detection of trypsin at nanomolar concentrations, which enables naked-eye detection. Importantly, this strategy can be employed for label-free, continuous assay for trypsin.

Conjugated poly(fluorene-quinoxaline) for fluorescence imaging and chemical detection of nerve agents with its paper-based strip.

Conjugated polymer of poly(fluorene-co-quinoxaline) was synthesized via Suzuki coupling polymerization. The emission color of the polymer can be tuned depending on the concentration of the polymer in solution. A low-energy bandgap is observed both in the concentrated solution and in the solid state, caused by aggregation of the polymer chains, resulting in long wavelength emission from the quinoxaline moiety, while short wavelength emission can be seen in diluted, well-dissolved solution. The presence of quinoxaline units enables us to demonstrate fluorescence switching and imaging. Paper-based strips containing the polymer are prepared via simple immersion of filter paper in the polymer solution for practical use in the detection of nerve agents. The emission of the paper-based strip is quenched upon exposure to diethyl chlorophosphate (DCP), a nerve agent simulant, and the initial emission intensity can be almost restored by treatment with aqueous sodium hydroxide solution, making a possible reversible paper-based sensor.

Fluorometric detection of lectin with water-soluble hyperbranched conjugated polymer using mannose mediation.

A water-soluble hyperbranched polymer containing boronic acid groups at the ends of the polymer, which are capable of binding to diol-containing mannose, was syntheized. The hyperbranched polymer was prepared by a palladium-catalyzed Suzuki cross-coupling reaction using the tribromo monomer for the hyperbranched type structure. The water-soluble hyperbranched polymer (HP) exhibited enhanced fluorescence intensity upon exposure to lectin in the presence of mannose compared to other proteins, such as lysozyme and cytochrome c, because mannose plays a key role in binding both lectin and HP resulting in selective sensing toward lectin.

Cobalt ion-mediated cysteine detection with a hyperbranched conjugated polyelectrolyte as a new sensing platform.

A highly efficient colorimetric and fluorescence turn-off probe for the sensitive and selective detection of the biologically important amino acid, cysteine (Cys), is demonstrated using a newly synthesized water-soluble hyperbranched polymer (HP) containing sulfonic acid groups. The detection mechanism involves two steps: (i) the slight quenching of HP in the presence of Co(2+) in advance; and (ii) the gradual quenching of the HP-Co(2+) complex according to the concentration of Cys due to the absorption screening effect of the formation of the Cys-Co(2+) complex, which prevents HP from absorbing excitation energy.

Highly selective cysteine detection and bioimaging in zebrafish through emission color change of water-soluble conjugated polymer-based assay complex.

A new concept for rapid, label-free cysteine sensing method is proposed via possible naked eye-detection of red-to-blue emission color change. Intermolecular exciton migration in conjugated polyelectrolyte-based assay complex is adopted to enhance selectivity and sensitivity for cysteine sensing by formation and dissociation of polymer-Hg(2+)-thymine assay complex in the absence and presence of cysteine, respectively. The assay complex shows red emission due to cooperative aggregation of conjugated polyelectrolyte, thymine, and Hg(2+). Upon exposure to cysteine, the assay complex dissociates into individual molecules showing transparent, blue-emitting solution, because cysteine extracts Hg(2+) from the assay complex via more favorable binding between cysteine and Hg(2+).

Simultaneous detection and removal of mercury ions in aqueous solution with fluorescent conjugated polymer-based sensor ensemble.

A water-soluble, sulfur-containing fluorescent conjugated polymer exhibits a visible fluorescence color change for detection of mercury in the presence of thymine. A new concept provides the design of a sensor ensemble using a simple combination method. This strategy avoids the need for complicated design and synthesis of a recognition group, eliminating the tedious synthetic efforts for the preparation of a sensor material.