Article pubs.acs.org/Macromolecules
A Free-Standing Self-Assembled Tubular Conjugated Polymer Sensor Seungwhan Oh, Kyungchan Uh, Seongho Jeon, and Jong-Man Kim* Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea S Supporting Information *
ABSTRACT: Tubular materials created by self-assembly of small organic molecules have gained great attention recently. Fabrication of tubular structures that have precise dimensions by using conventional self-assembly approaches is extremely challenging. Herein we describe fabrication of a free-standing tubular polydiacetylene (PDA) sensor based on the meniscusguided self-assembly and polymerization of diacetylene (DA) monomers. The free-standing single PDA tube can be utilized as an unprecedented microcapillary-based sensor system, which requires only a minimum amount (70−140 nL) of an analyte solution. We have observed 4 orders of magnitude more sensitive to analytes than is a conventional PDA sensor when a biotinfunctionalized PDA tube is exposed to streptavidin. The microcapillary-based analytical method developed in this study should find great utility not only for PDA sensors but also for other free-standing wire sensor systems.
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and (2) self-assembly of macrocyclic DAs.36−38 Regardless of their structures, the monomer precursors inevitably generate nonuniform tubular PDAs when conventional self-assembly methods are employed. The reason for this is that control over dimensions of the tubular structures during the self-assembly process is extremely difficult. In addition, fabrication of a single tubular PDA is more challenging because these materials tend to exist as tubular aggregates. The limitations associated with current methods have encouraged us to develop a more reliable approach for the preparation of tubular PDAs. Studies addressing this issue, which are part of our continuing efforts in the area of PDAbased smart materials,39−41 has led to the design of a new meniscus-guided solidification procedure42−44 that can be utilized to fabricate a free-standing, stimulus-responsive, single microtubular PDA. The most significant feature of the methodology developed in the current investigation is that it can be employed to construct a highly efficient and sensitive PDA sensor. Specifically, a microcapillary tube that is used for fabrication of functionalized PDA can be loaded with an analyte solution. The solution (70−140 nL) within the microcapillary tube contains confined analyte molecules that can engage in efficient interactions with surface functional groups on the PDA. In addition, confinement within the microcapillary tube prevents fast evaporation of the analyte solution and consequently provides a sufficient amount of time (3−6 h) for the processes involved in the analysis to take place. The results of this study also show the viability of a functionalized PDA microtubular sensor and that the sensor is greater than 4 orders of magnitude more sensitive than a related conventional solution-based sensor.
INTRODUCTION A great effort has been made to develop bio-inspired supramolecular structures by taking advantage of the selfassembly phenomenon.1−5 Diverse one-dimensional supramolecular architectures including wires6−8 and tubes9−12 have been created through self-assembly of functional organic molecules. Even more interesting is the fact that introduction of selectively designed functional units into these organic molecules can be employed to create self-assembled structures that have unique functions. A prototypical example of this type of material is a polydiacetylene (PDA),13−20 a supramolecular conjugated polymer that is prepared by polymerization of selfassembled lipids bearing conjugated diacetylene (DA) moieties in the middle of alkyl chains. Strong interchain interactions existing in the ordered structures of the PDA cause extensive and efficient overlap of p-orbitals in an alternating ene−yne backbone. As a result, PDAs typically absorb visible light with maximum at around 650 nm that corresponds to a blue color. Disruption of the ordered conjugated structure by various chemical/biochemical and physical stimuli often results in a hypsochromic shift of the absorption maxima of the PDA to around 550 nm corresponding blue-to-red color change. In addition to the brilliant color change, fluorescence turn-on accompanies the phase transition because the blue-phase PDAs are virtually nonfluorescent while the red-phase counterparts emit red-color fluorescence. The stimulus-responsive color and fluorescence changes of PDAs have served as physical bases for the design of efficient colorimetric and fluorometric sensing systems.21−31 The unique structural and optical features of PDAs, derived by polymerization of self-assembled DA monomers, have stimulated investigations aimed at assessing the possibility of forming tubular PDAs. In general, tubular PDAs can be prepared by using two different approaches including (1) selfassembly of amphiphilic DAs in aqueous environments32−35 © XXXX American Chemical Society
Received: June 26, 2016 Revised: August 1, 2016
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DOI: 10.1021/acs.macromol.6b01345 Macromolecules XXXX, XXX, XXX−XXX
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Scheme 1. Chemical Structures of Diacetylene Monomers Used in the Fabrication of Polydiacetylene Microtubes PCDA, ECDA, DCDDA, PCDA-NH2, and PCDA-Biotina
a
PCDA = 10,12-pentacosadiynoic acid, ECDA = 5,7-eicosadiynoic acid, and DCDDA = 10,12-docosadiyndioic acid.
Figure 1. (a) Schematic illustration of a growing a diacetylene (DA) nanotube by using the meniscus guided method. (b, c), SEM images of the PCDA-derived PDA microtubes obtained after 254 nm UV irradiation (1 mW/cm2, 20 s) of the vertically grown DA microtubes on silicon substrate. (d) Microscopic images of a fluorescein filled PDA tube obtained by using excitation at 495 nm (left), 595 nm (middle), and the merged image (right). Scale bar: 4 μm. (e) Optical microscopic images that show formation of a free-standing PCDA tube. Scale bar: 8 μm. (f−i) Schematic illustration of PDA tube formation by using the meniscus-guided method. (f) DA monomers inside the wire are randomly oriented during the growing step. (g) DA monomers move toward the edge of the wire and self-assemble to form a tubular structure during rapid solvent evaporation. (h) Formation of an entire DA tube after the solvent evaporation step. (i) UV-induced photopolymerization of the DA tube results in the generation of the PDA tube.
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literature procedures. FITC-labeled streptavidin and unlabeled streptavidin were purchased from Sigma-Aldrich (St. Louis, MO). Characterization. Various microscopic techniques were employed to characterize the properties of tubular diacetylene (DA) wires. A phase contrast optical microscope equipped with either a Nikon DS-
EXPERIMENTAL SECTION
Materials. The DA monomers 10,12-pentacosadiynoic acid (PCDA), 5,6-eicosadiynoic acid (ECDA), and 10,12-docosadiyndioic acid (DCDDA) were used as received from GFS Chemical (Powell, OH). PCDA-NH250 and PCDA-Biotin51 were prepared using B
DOI: 10.1021/acs.macromol.6b01345 Macromolecules XXXX, XXX, XXX−XXX
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Macromolecules Fi2 or a Nikon CX-10C with OFN25 WD11 coaxial zoom lens was used to monitor fabrication of tubular DA wires. Visualization of the tubular DAs was assisted by using NIS-Elements D 4.20.00 software. Images were recorded on an Olympus BX51 microscope with DP70 CCD camera at 100× lens. Fluorescence microscopic images of tubular PDAs after exposure to FITC labeled streptavidin were recorded with a confocal fluorescence microscope (Olympus IX83 microscope) with 488 nm laser excitation through FITC excitation filter controlled by FV10-ASW 4.0 software. Raman spectra were recorded on a LabRAM HR Evolution Raman spectrometer (Horiba Scientific, 785 nm laser source). SEM images were obtained on a Hitachi s4800 FE-SEM with a tilt angle of 45°, and Pt coating (Hitachi E1045) was used to achieve higher quality images. XRD spectra were recorded with a HR-XRD, D8 Discover, Bruker. Fabrication of Tubular Polydiacetylene (PDA) Wires. A typical procedure for the preparation of a tubular PDA wire is as follows. A solution (1 mL) of 10,12-pentacosadiynoic acid (PCDA) (10 mg) in N,N-dimethylformamide (DMF) was loaded into a capillary tube (tip diameter: 1 μm; length: 50 mm). The capillary is produced using a micropipet puller (Micropipet Puller Model P-97, Sutter Instrument Co.) from standard wall borosilicate tubes (o.d.: 1.00 mm; i.d.: 0.75 mm; 10 cm length). The tip diameter can be controlled to have an i.d. of 1−5 μm. After removal of the air bubbles, the capillary containing the PCDA solution was mounted into a homemade meniscus guided solidification device. The writing system, housed on a vibration isolation table, consists of dc motor driven platforms (PK5438WH100S) capable of moving the stage (X, Z directions) and capillary tip (Y, Z directions) using a controller from Inno Optics. Capillary tip speeds from 0.1 to 100 μm/s are achievable and dynamically controllable during the process. Platinum-coated silicon wafers (Sputtered using a Hitachi E1045) were used as the substrate. Slow pulling (1 μm/s) of the micropipet containing a DMF solution of DA results in the generation of a vertically grown tubular DA wire with a diameter of ca. 1 μm. Irradiation of the DA monomer wire with UV light (254 nm, 1 mW/cm2, 20 s) results in the generation of a blue tubular PDA wire. Biotin-Functionalized Tubular PDA−Streptavidin Interaction. A microcapillary tube containing a streptavidin solution (1− 1000 ng/mL) in deionized water was placed above a biotinfunctionalized tubular PDA wire (diameter: 2 μm; length: 20 μm). The biotinylated PDA tube was prepared by employing the strategy described above with DA and DA-Biotin (40:1 wt ratio) as the monomers. The capillary tube was slowly moved down toward the PDA tube until the tube was immersed in the streptavidin solution (see Figure 4b). After 30 min incubation, the capillary tube was removed from the tube, and the tube was washed with deionized water to remove unbound streptavidin (5 × 5 min). Fluorescence emission from the PDA tube was measured, and the red intensity value was obtained using a Photoshop program. For comparison, a similar process was repeated using a PCDA derived PDA tube that contains no surface biotin moieties.
diyndioic acid (DCDDA), as well as amine-functionalized PCDA-NH2 and the biotinylated DA monomer PCDA-Biotin, can also used for the formation of tubular DAs (vide inf ra). Figure 1a contains a schematic representation of the process involved tubular DA formation and polymerization. As shown, slow meniscus guided pulling (1 μm/s) of a micropipet (tip radius: 1.0 μm) containing a DMF solution of PCDA (10 mM) results in generation of a vertically grown PCDA wire (Figure 1b). Interestingly, SEM analysis of the PCDA wire indicates that it has a tubular structure with a thickness in the range of 100−200 nm and an open aperture (Figure 1c). Analysis of the results of repeated fabrication processes reveals that only microtubular forms are produced. Owing to its direct writing compatibility, the meniscus-guided solidification method can be used to grow DA microtubes with controllable length and diameter. Because of its dependence on pulling rates, lengths of DA microtubes in the range of 10−50 μm can be readily produced (Figure S1). In addition, the outer diameters (o.d.) of the PDA tubes are governed by the tip radius of the micropipet. As expected, DA microtubular wires of larger o.d. 1−6 μm are produced when micropipets with larger tip radii are employed (Figure S2). A fluorescent dye encapsulation study was carried out to demonstrate that tubular structures are generated by using the new method (Figure 1d). For this purpose, a PCDA wire, produced by using the procedure described above, was irradiated with 254 nm UV light to induce polymerization. The resulting PDA wire was heated to promote its transition to the fluorescent red-color form. Fluorescence microscopic images were then recorded on the heat-treated PDA wire following exposure to a fluorescein solution. As seen by inspection of Figure 1d, typical green fluorescein derived fluorescence is observed when the fluorescein-treated PDA wire is irradiated by using 495 nm light (Figure 1d, left). Irradiation of the fluorescein loaded wire with 595 nm light results in generation of a red-color fluorescence emanating from the redphase PDA (Figure 1d, middle). By merging the two fluorescence images, it can be clearly seen that the fluorescein molecules are located inside the tubular PDA structure (Figure 1d, right). The formation of the tubular DA structure can be easily visualized by looking at the video clip provided as Supporting Information (Movie 1). Also, the images displayed in Figure 1e demonstrate that tubular DA forms immediately as the microcapillary tip separates from the wire. The changes in the brightness indicate that the solvent molecules trapped inside the tubular wire escape completely within 1.6 s to yield the tubular structure. The “0 s” in Figure 1e means that the image was captured immediately after the capillary was pulled from the wire. The generation of free-standing PDA nanotubes by using the meniscus guided solidification method schematically illustrated in Figure 1f−i is interesting from several perspectives. In the process, when the meniscus of the solution is slowly pulled upward using a micropipet after it touches the surface, DA monomers begin to crystallize near the meniscus edge to form walls of the tube. The DA monomers inside the tube are randomly oriented during the pulling event (Figure 1f). The organic solvent inside the tube evaporates rapidly when the micropipet is completely pulled away from the growing wire (Figure 1g), and a tubular DA wire is generated when the organic solvent is completely lost (Figure 1h). Finally, photoirradiation with 254 nm UV light polymerizes the DA monomers to create a PDA microtube (Figure 1i). By
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RESULTS AND DISCUSSION Fabrication of Microtubular PDA Wire. A key feature of the new approach for fabrication of a free-standing tubular PDA is that it relies on solidification of DA monomers through evaporation of an organic solution being pulled from a microscale meniscus. As a result, a single vertical tubular DA wire can be generated at room temperature by guiding the meniscus upward using a micropipet. The initial phase of this investigation focused on utilizing this approach to generate a free-standing PDA microtube using 10,12-pentacosadiynoic acid (PCDA) as the DA monomer (Scheme 1). Importantly, PCDA is a commercially available substance that has been widely investigated as a monomer for the construction of functional PDAs. It should be noted that other DA monomers, including 5,7-eicosadiynoic acid (ECDA), which has a shorter alkyl chain than PCDA, and bolaamphiphilic 10,12-docosaC
DOI: 10.1021/acs.macromol.6b01345 Macromolecules XXXX, XXX, XXX−XXX
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Figure 2. Pairs of optical (left) and fluorescence (right) microscopic images of a PCDA-derived DA microtube as prepared (a), after 254 nm UV irradiation (1 mW/cm2, 20 s) (b), and after heat treatment (65 °C, 10 min) (c) of the UV-irradiated DA tube. Scale bar: 8 μm. (d) Raman spectra of a PCDA powder (black line), a tubular PCDA wire after 254 nm UV irradiation (1 mW/cm2, 20 s) (blue line), and after heat treatment (65 °C, 10 min) (red line) of the UV irradiated PCDA tube. Owing to facile polymerization of tubular PCDA under ambient light and during Raman data collection, the spectrum for monomeric PCDA was recorded in a powder state. (e) X-ray diffraction spectrum of PCDA-derived PDA crystals. (f) A proposed molecular packing of PDA.
Figure 3. (a) Schematic representation of reaction between an amine-functionalized PDA tube and fluorescamine. (b) Optical and fluorescence microscopic images of fluorescamine exposed (10 mM, 1 min) PDA microtubes derived from a 1:1 (by wt ratio) mixture of PCDA and PCDA-NH2. (c) Optical and fluorescence microscopic images of fluorescamine exposed (10 mM, 1 min) PDA microtubes derived from PCDA. The generation of green fluorescence in (b) is strong evidence of formation of amine−fluorescamine adducts on the surface of the tube. The PDA tube obtained with only PCDA shows no fluorescence emission as in (c) (excitation: 495 nm).
can be readily visualized using a fluorescence microscope (Figure 2c, right). The nature of the PDA formed in the tubular wire was probed by using Raman spectroscopy. As displayed in Figure 2d, the acetylenic band of the DA monomer occurs at 2257 cm−1 (black line). The Raman spectrum of the blue phase tubular PDA wire, obtained from UV irradiation of the monomeric tubular DA wire, contains bands associated with conjugated alkyne and alkene groups at 2085 cm−1 (CC) and 1459 cm−1 (CC), respectively (blue line). In contrast, the Raman spectrum of the red-phase PDA, obtained by heating
employing this strategy, tubular PDAs from several DA monomers can be readily fabricated (Figure S3). Structural Analysis of Mirotubular PDA Wire. Formation of the PDA tube can be easily verified by using optical microscopy because the colorless DA containing tube (Figure 2a, left) turns to blue (Figure 2b, left) upon UV irradiation. Heating a blue-phase PDA microtube at 65 °C for 10 min results in generation of a red-phase PDA microtube (Figure 2c, left). Because the monomeric DA and blue-phase PDA microtubes are virtually nonfluorescent (Figure 2a, right, and 2b, right), heat promoted fluorescence turn-on of the PDA tube D
DOI: 10.1021/acs.macromol.6b01345 Macromolecules XXXX, XXX, XXX−XXX
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Figure 4. (a) Schematic representation of a free-standing tubular PDA sensor. The PDA microtube is exposed to an analyte solution that is confined in a microcapillary tip. (b) Optical microscopic images of a free-standing biotinylated PDA microtube and a microcapillary tube that contains a streptavidin solution (ca. 100 nL). The sequential approach−dip−interact−remove process allows efficient analysis using a minimum amount of analyte solution. (c) Optical (left) and fluorescence (middle: excitation at 495 nm; right: excitation at 595 nm) microscopic images of a biotinfunctionalized PDA tube after exposure to a FITC-labeled streptavidin solution (100 ng/mL). (d) Optical (left) and fluorescence (excitation at 495 nm) microscopic images of a PCDA-derived PDA tube after exposure to a streptavidin solution (100 ng/mL). (e) Optical (left) and fluorescence (excitation at 495 nm) microscopic images of a biotin-containing PDA tube after exposure to a streptavidin solution (100 ng/mL). Scale bars in (b− e): 8 μm.
Microtubular Polydiacetylene Sensor. An interesting feature of the free-standing PDA tube, generated in the manner described above, is the possibility that it can be used in the design of unique and an unprecedented PDA-based sensor systems. As shown in Figure 4a, the microcapillary tube can be utilized as a reservoir for a solution of an analyte. As a result, functionality on the walls of the tubular PDA can interact with target analyte molecules in the solution that is confined in the microcapillary tube. If practical, this type of microcapillary tube based sensor system would require only a tiny amount (70− 140 nL) of analyte solution. This would be an exceptionally advantageous feature because conventional solution-based sensor formats require relatively large amounts of analyte solutions (100−1000 μL). In addition, because the analyte solution is confined in the microcapillary tube, evaporation of the solvent should be slowed. This property would lengthen the time (3−6 h) required to carry the process used for the assay. This would be another meritorious feature of the system because use of conventional PDA-immobilized sensor chips is greatly limited by fast evaporation of the solvent when the analyte solution is deposited on the surface of the sensor. A biotin−streptavidin interaction was employed to explore the viability of a microcapillary tube-based assay system. First, the optical microscopic images given in Figure 4b were used to show the sequence of events that occur when a PDA microtube is approached by a microcapillary tube containing a solution. Next, a biotin-functionalized free-standing PDA tube, derived from a mixture of PCDA and PCDA-Biotin (40:1, by weight), was exposed to a micropipet delivered, fluorescent FITClabeled streptavidin solution for 30 min. The monomer ratio was optimized based on the efficiency for the formation of the tube and sensitivity of the resultant PDA tube. Although the color change taking place is difficult to observe with an optical microscope (Figure 4c, left), inspection of the fluorescence microscopic images of the FITC-treated PDA tube shows that green (Figure 4c, middle, excitation at 495 nm) and red (Figure 4c, right, excitation at 595 nm) fluorescence are generated. The lack of an analogous red fluorescence response using tubular PDA obtained from only PCDA (Figure 4d, right, and Figure
(red line), contains higher frequency alkyne and alkene bands at 2116 and 1521 cm−1, respectively. In order to obtain information about the molecular structure of the tubular PDA, X-ray diffraction (XRD) studies were carried out with PDA crystals obtained under conditions that are similar to those used for tubular PDA formation. The XRD spectra of the PDA (Figure 2e), prepared by polymerization of PCDA that is crystallized from a DMF solution, contains bands associated with well-ordered lamellar structures. By assigning the Bragg diffraction peaks in the range of 2θ = 1.84°−16.9° to (100), (200), ..., (l00) (from left to right, Figure 2e), the interlayer periodicity can be calculated using the expression d = ldl00. Using this equation, the average interlayer periodicity is calculated to be ca. 47.81 Å. Based on this information, the PDA lamella structure shown in Figure 2f has a separation distance (d) of about 3.89 Å, which satisfies the geometric requirement for PDA formation. The presence of surface carboxylic acid groups in the PDA tube derived from PCDA was demonstrated by exposing the tube to an aqueous NaOH solution (Figure S4). It is known that PDA supramolecules containing surface carboxylic acid headgroups undergo a colorimetric transition when placed in a high pH medium owing to the repulsive interactions that take place in conjunction with carboxylate ion formation.45 The PCDA-derived PDA tube was observed to display a blue-to-red color transition along with a fluorescence turn-on when placed in aqueous NaOH. Moreover, that the PDA tube derived from the amine-containing DA monomer PCDA-NH2 (Scheme 1) possesses surface amine moieties can be readily demonstrated by treatment of the tube with a fluorescamine solution (Figure 3). Fluorescamine is well-known to form a fluorescent adduct with a primary amine and has been widely investigated as a probe molecule for a primary amine (Figure 3a).46 Fluorescamine is nonfluorescent and emits green fluorescence upon amine-fluorescamine adduct formation. The generation of green fluorescence shows that the amine−fluorescamine adduct forms on the surface of the PDA tube (Figure 3b, right). The PDA tube obtained with only PCDA shows no fluorescence emission (Figure 3c, right). E
DOI: 10.1021/acs.macromol.6b01345 Macromolecules XXXX, XXX, XXX−XXX
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Figure 5. (a) Red intensity as a function of streptavidin concentration. (b) Raman spectra of a biotinylated PDA tube before (blue line) and after (red line) exposure to streptavidin (100 ng/mL) for 30 min. (c) Schematic representation of the interaction between a biotin-functionalized PDA microtube and streptavidin.
PDA backbone, which causes partial distortion of the conjugated π-system and the consequent blue-shift of the absorption maximum.
S5) confirms the existence of a biotin specific interaction with the FITC-labeled streptavidin. In order to prove that the red emission arises from a streptavidin promoted blue-to-red phase transition of the PDA-Biotin tube, we probed the response arising by addition of a solution of FITC-unlabeled streptavidin to the PDA-Biotin tube. As expected, red fluorescence was observed (Figure 4e, right). The ability of the PDA-Biotin microtube to detect streptavidin in a concentration-dependent manner was probed next. In Figure 5a are displayed red intensities developed in the PDA-Biotin microtube as a function of streptavidin concentration in the analyte solution. The biotin-functionalized tubular PDA wire was found to display a streptavidin concentrationdependent increase in its red fluorescence intensity with a streptavidin detection limit of 1 ng/mL. This detection limit is remarkably low in contrast to that of biotin-functionalized colorimetric (2.5 μg/mL)47,48 and fluorometric (1.2 μg/mL)49 PDA sensors reported to date. The significant, over 4 orders of magnitude increase in the sensitivity of the newly developed tubular PDA sensor is difficult to understand fully. However, it possibly results from the synergic effect of both the unique tubular structure and the confined nature of the analyte solution. Binding of streptavidin molecules to biotin on the PDA surface results in transfer of a significant amount of mechanical energy to the PDA backbone, which causes partial distortion of the conjugated system and the consequent blueshift of the absorption maximum and fluorescence turn-on feature. The streptavidin promoted blue-to-red phase transition of the PDA-Biotin microtube was further explored using Raman spectroscopy. As the spectra displayed in Figure 5b show, the streptavidin induced blue-to-red transition of biotin-functionalized tubular PDA wire occurs concurrently with shifts of alkyne−alkene bands Raman bands from 2081 and 1454 cm−1 to 2118 and 1517 cm−1, respectively. These phenomena are typical for blue-to-red phase changes of PDAs. In Figure 5c is given a schematic illustration of the interaction between a biotin-functionalized PDA tube and streptavidin. Binding of streptavidin molecules to biotin on the PDA surface results in transfer of a significant amount of mechanical energy to the
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CONCLUSION In conclusion, the effort described above led to the development of a method to fabricate a single PDA microtube. The process is initiated by meniscus-guided solidification that causes efficient formation of a free-standing tubular DA wire. Generation of the tubular structure originates from the coffee ring effect and is maintained during pulling up of a micropipet that contains a DA solution. Crystallization and formation of a wall of DA monomers inside the tube take place during solvent evaporation and produces a rigid free-standing DA microtube. Photopolymerization of the DA tube results in the generation of a blue phase PDA microtube. The ability of the free-standing tubular PDA to serve as a sensor platform was demonstrated by using interaction of a PDA-Biotin tube with streptavidin. The sensitivity for detection of streptavidin by this sensor is 4 orders of magnitude greater than that of a conventional solution-based PDA assay system. The microcapillary-based analytical method developed in this study should find great utility not only for PDA sensors but also for other free-standing nano/micro wire sensor systems.
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ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.macromol.6b01345. Images of PDA microtubes with various lengths, plots of tube diameter, PDA microtubes from various diacetylene monoemrs, PDA microtube after treatment with a NaOH or FITC-labeled streptavidin solution; 1H NMR data for synthetic diacetylene monomers PCDA-NH2 and PCDA-Biotin (PDF) Movie 1 (AVI) Movie 2 (AVI) F
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AUTHOR INFORMATION
Corresponding Author
*E-mail:
[email protected] (J.-M.K.). Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS The authors gratefully thank National Research Foundation of Korea (NRF) for financial support through Basic Science Research Program (No. 2014R1A2A1A01005862).
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