A Magnetically Responsive Polydiacetylene Precursor for Latent

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A Magnetically Responsive Polydiacetylene Precursor for Latent Fingerprint Analysis Joosub Lee,† Chan Woo Lee,*,‡ and Jong-Man Kim*,†,‡ †

Department of Chemical Engineering, Hanyang University, Seoul 133-791, Korea Institute of Nano Science and Technology, Hanyang University, Seoul 133-791, Korea

‡

S Supporting Information *

ABSTRACT: A magnetically responsive diacetylene (DA) powder was developed for the visualization of latent fingerprints. A mixture of the DA and magnetite nanoparticles, applied to a surface containing latent fingermarks, becomes immobilized along the ridge patterns of the fingerprints when a magnetic field is applied. Alignment along the ridge structures is a consequence of favorable hydrophobic interactions occurring between the long alkyl chains in the DAs and the lipid-rich, sebaceous latent fingermarks. UV irradiation of the DA−magnetite composite immobilized on the latent fingerprint results in the generation of bluecolored PDAs. Heat treatment of the blue-colored image promotes a blue-to-red transition as well as fluorescence turn-on. A combination of the aligned pale browncolored monomeric state, UV irradiation generated blue-colored PDA state, as well as the heat treatment generated red-colored and fluorescent PDA state enables efficient visual imaging of a latent fingerprint, which is deposited on various colored solid surfaces. KEYWORDS: polydiacetylene, conjugated polymer, latent fingerprint, magnetic nanoparticle, fingerprint analysis

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INTRODUCTION Polydiacetylenes (PDAs),1−11 supramolecular conjugated polymers, have received great attention as chemosensors because they display stimulus-responsive color (generally blue-to-red) and fluorescence (non-to-red) changes. A wide range of chemical/biochemical (organic solvent,12−20 ions,21,22 surfactants/alkyl amines,23−26 specific molecular recognition,27−36 explosives37) and physical (temperature,38−45 mechanical strain,46−48 magnetic field,49 electric current50−52) stimuli cause colorimetric and fluorometric transitions of properly designed PDAs. Colorimetrically responsive PDAs also can be created to respond to pure water by introduction of hygroscopic elements into the headgroup of the precursor diacetylene (DA) monomers53 or by embedment of the PDA in a hydrogel matrix.54 In addition to colorimetric sensing, PDAs have been used as imaging materials. For instance, Mackiewicz et al. reported a new in vivo tumor imaging system that employs surface functionalized PDA vesicles.55 Application of PDAs to imaging of latent fingermarks was also described,56,57 as exemplified by the results of studies by Miller and Patel56 in which a mixture of 2,4-hexadiyne-1,6-bis(phenylurethane) (HDDPU) and 2,4hexadiyne-1,6-bis(p-chlorophenylurethane) (HDDCPU) was employed to image latent fingerprints. Visible fingerprints can also be observed when an acetone solution containing the two diacetylenes is sprayed over latent fingermarks on nonporous solid substrates. The success of these imaging systems is a consequence of the fact that diacetylene cocrystals, formed along oily ridge structures on fingerprints, are nonpolymeriz© XXXX American Chemical Society

able, while those generated between ridge impressions (background surfaces) are polymerizable. As a result, a redpurple PDA forms on background surfaces and while the ridges remain colorless to the naked eye. More recently, Reedy and co-workers 57 investigated the meritorious features and limitations of the cocrystallization approach developed by Miller and Patel. In this effort, latent fingermarks were deposited on a variety of porous and nonporous solid substrates. We envisioned that incorporation of additional meritorious features into the current PDA-based fingerprint imaging system would make the method more informative and attractive for practical use. Two, conceptually new features that would enhance this fingerprint imaging technique are (1) the facile introduction of magnetic nanoparticles and (2) the utilization of fluorescence from the red-phase PDA. A combination of the two features should enable highly efficient visualization of latent fingermarks58−67 deposited on various solid surfaces. The results of an investigation verifying the advantages of incorporating these features are described below.

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EXPERIMENTAL SECTION

Materials and Instruments. 10,12-Pentacosadiynoic acid (PCDA) was purchased from GFS Chemicals, Ohio, USA. Iron(III) chloride hexahydrate (FeCl3·6H2O) and iron(II) sulfate heptahydrateReceived: January 15, 2016 Accepted: February 19, 2016

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DOI: 10.1021/acsami.6b00566 ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX

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ACS Applied Materials & Interfaces (FeSO4·7H2O) were purchased from Simga-Aldrich. Poly(ethylene glycol) (PEG, Mw = 600 g mol−1) was purchased from Fluka. A NdFeB (10 × 10 mm2) magnet with a surface field strength of 5030 G was used for visualization of latent fingerprints. Scanning electron microscope (SEM) images were obtained using a JEOL (JSM-6330F) FE-SEM at an accelerating voltage of 15 kV. Each sample was coated with Pt for 30 s before analysis. Synthesis of Magnetic Nanoparticles. Magnetite nanoparticles were synthesized using the known procedure.68 Briefly, FeCl3·6H2O (4.87g) and FeSO4·7H2O (3.37g) were added to 130 mL of deionized water, followed by addition of 25 g of PEG. The resulting solution was stirred at 78 °C, and the pH of the solution was adjusted to 9 by addition of a dilute aqueous ammonia hydroxide. The resulting mixture was stirred at 78 °C for 24 h. The formed Fe3O4 nanoparticles were collected by filtration, washed with deionized water, and dried under vacuum to afford 2.24 g (53%) of the desired magnetite nanoparticles. Preparation of Diacetylene−Magnetite Composites. A typical procedure for the fabrication of a diacetylene−magnetite composite is as follows. A mixture of 10,12-pentacosadiynoic acid (1.0 g) and magnetic nanoparticles (500 mg) in tetrahydrofuran (10 mL) was gently grinded in a crucible until the solvent evaporates completely. Development of Latent Fingerprint. A sebaceous latent fingerprint was prepared by rubbing a fingertip over the forehead, and a latent fingerprint was deposited on a solid substrate by pressing the fingertip. Magnetically active diacetylene powder was casted over the latent fingermark. Immobilization of the diacetylene−magnetite composite on the latent fingerprint image was achieved by gently moving a magnet under the solid substrate where the latent fingermark is deposited. Excess diacetylene−magnetite composite powder was removed by softly blowing with an air blower. UV light (254 nm, 1 mW/cm2) was used to irradiate the diacetylene-immobilized image for 10−30 s to induce photopolymerization. Heat treatment was carried out to convert the blue-phase PDA to a red-phase one.

Figure 1. Photographs of the magnetic PCDA powders obtained using different weight ratios of PCDA and MNP ((A) as prepared, (B) after UV irradiation (254 nm, 1 mW/cm2) for 30 s, (C) after heat treatment (80 °C, 20 s) of the samples in (B)).

as the amount of magnetic nanoparticles increases, differentiation of color changes occurring during the UV induced polymerization and heat treatment as well as the magnetic response stages is difficult. Optimal differentiation is attained when the weight ratio between the monomer and magnetic nanoparticles is 20:1 or 40:1 (PCDA:MNP), respectively. Visualization of color changes taking place on formation and heat treatment of the PDA is difficult when a 2:1 or 10:1 weight ratio is utilized. Although vivid color changes can be monitored using a sample derived from a 100:1 weight ratio, a weak magnetic response makes the composite less effective for the imaging. Sebaceous latent fingerprints were obtained from volunteers by rubbing their fingers on their foreheads and then gently pressing them on paper. In order to visualize the latent fingerprint, the magnetically active PCDA−MNP composite powder was scattered onto the surface of the paper containing the latent fingerprint. A magnetic bar was then placed under the fingermark on the paper, and the paper was gently shaken to enable immobilization of the magnetically active DA powder on the latent fingerprint. Following removal of excess nonimmobilized powder by using gently blowing air, the area containing the latent fingerprint on which the magnetite−DA powder is immobilized was irradiated with a hand-held laboratory UV lamp (254 nm, 1 mW/cm2) for 30 s. This process causes the initially invisible latent fingerprint (Figure 2A, left) to become blue-colored and visible to the naked eye as a result of the formation of the PDA (Figure 2A, middle). The blue-colored PDA image becomes red upon heat treatment (80 °C, 20 s) (Figure 2A, right). As stated above, the most discernible latent fingerprint image is obtained when the weight ratio of the PCDA to MNP is 20:1. Because red-phase PDAs are fluorescent, the well-resolved friction ridge patterns of the latent fingerprint can be observed using a fluorescence microscope (Figure 2B). As a consequence of the fact that a latent sebaceous fingermark is abundant in fatty acids, favorable hydrophobic interactions between these molecules and lipid like DA molecules facilitates immobilization of the DA on

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RESULTS AND DISCUSSION The magnetically active DA powder used for the visualization of latent fingermarks was prepared by grinding a mixture of magnetite and DA monomer. 10,12-Pentacosadiynoic acid (PCDA), which is commercially available, was employed as the polymerizable DA monomer. Owing to the dominant dark brown color of the magnetic nanoparticles, optimization of the ratio between the magnetic nanoparticles and the monomer was necessary in order to visualize color changes. When the magnetic nanoparticles are present in excess, monitoring of color change is difficult, whereas, when the amount of magnetic nanoparticles is too small, the composite is magnetically inactive. Accordingly, a balanced ratio between the two components is essential for the good visualization of the latent fingermarks. In initial studies, the PCDA−MNP composite was prepared by mixing the two components in their solid states. However, using this approach led to generation of an aggregated composite powder that is ineffective for latent fingerprint imaging. To solve the problem, a slightly different approach was employed. Specifically, the DA monomer and magnetic nanoparticles were dispersed in a minimum amount of THF. Grinding of the dispersed material was carried out until the solvent evaporated completely. This method enabled efficient generation of uniformly dispersed magnetic PCDA particles, which are suitable for latent fingerprint imaging. In Figure 1 are shown photographs of the PCDA−magnetite composite powders initially prepared (Figure 1A), after 254 nm UV irradiation (254 nm, 1 mW/cm2, 30 s) (Figure 1B), and following heat treatment (80 °C, 20 s) of the UV irradiated composite (Figure 1C). By viewing these images, it is clear that, B


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fingerprint ridge structures. In fact, the high quality of the fingerprint images obtained using this technique enables visualization of second level bifurcation, crossover, termination, and lake structures (Figure 2C). It should be noted that latent fingerprint images can be obtained without using the magnetic nanoparticles as displayed in Figure S1 (Supporting Information). The resolution of the images, however, is lower than that of fingerprint images obtained using the magnetic PCDA particles. This is presumably due to the fact that pure PCDA particles tend to form aggregates while the PCDA−MNP composite does not form large aggregates. In addition, the imaging process with the PCDA−MNP composite can be readily achieved by using a magnetic bar while immobilization of PCDA powder requires a careful brushing process to avoid overcoating of the imaging material. In Figure 3 are shown scanning electron microscopic (SEM) and transmission electron microscopic (TEM) images of magnetically active PDAs that are immobilized on latent fingermarks. Inspection of the SEM image in Figure 3A demonstrates that the magnetic PDA powders selectively adhere along the ridge patterns. A magnification of the SEM image reveals that the PDA microcrystals exist (Figure 3B), and closer inspection of the individual microcrystals reveals that the magnetic nanoparticles (15−40 nm) are attached to the surface of PDA particles (Figure 3C). The SEM image (Figure 3D) obtained on material that does not contain PDAs shows the presence of only a lipid-covered morphology, confirming that the particles seen in the image in Figure 3B are from magnetic PDAs. The versatility of magnetically responsive PCDA as latent fingerprint imaging materials was demonstrated by its application to visualization of latent fingermarks deposited on various surfaces, including aluminum foil, PET film, and glass substrates. For example, heat treatment of a PDA, which is

Figure 2. (A) Photographs of visualized latent fingerprints obtained using magnetic PCDA powder (left), and the image after 254 nm UV irradiation (middle) for 10 s, and after heat treatment (80 °C, 20 s). The schematic illustrations represent the diacetylene monomer, polydiacetylene, and heat stimulated polydiacetylene. (B) Fluorescence images of sebaceous latent fingerprints on paper obtained with magnetically active PCDA. (C) Magnified fluorescence images of fingerprints showing specific patterns including bifurcation (1), crossover (2), termination (3), and lake (4).

Figure 3. (A) SEM image of a latent fingerprint developed by using the magnetic PDA. (B) Magnified SEM image of the magnetic PDA particles in the immobilized region of the latent fingermark. (C) TEM image of an individual PDA−MNP composite particle. Magnetic nanoparticles attached to the PDA particle are visible in the TEM image. (D) SEM image of a latent fingermark without immobilization of magnetic PDA particles. C


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Figure 4. (A) Photograph of a latent fingerprint obtained after UV irradiation (254 nm, 1 mW/cm2) for 10 s and subsequent heat treatment (80 °C, 20 s) of the magnetically active PCDA-coated latent fingermark which is deposited on an aluminum foil. (B) Fluorescence image of the magnetically active PDA-derived heat-treated latent fingerprint deposited on an aluminum foil. (C) Magnified fluorescence images showing specific patterns including bifurcation (1), termination (2), and sweat pores (1, 2).

coated on a latent fingerprint on the surface of aluminum foil by using this procedure, results in the generation of a fluorescence microscope detectable image (Figure 4) containing clear ridge patterns. Second level structures such as bifurcation, termination, and some pores are clearly visible in this image. In fingerprint visualization methods, it is important to have the color of the dusting powder compatible with that of the substrate on which the latent fingerprint is deposited. Accordingly, a dusting powder that has the same color as that of the background of the substrate is not useful. Crime investigators often use dusting powders that are mixed with white- and black-colored materials to enhance their effectiveness in use with both light- and dark-colored substrates. In this respect, the magnetically responsive diacetylene powder is attractive as a latent fingerprint imaging material because it undergoes distinct color changes upon UV irradiation and subsequent heat treatment. Especially interesting is the fluorescence emitted from the red-phase PDA because it better enables visualization of ridge patterns in the event that a clear optical image cannot be obtained. For instance, it is difficult to see clearly second level structures using the optical microscopic images (Figure 5B−D) when latent fingermarks (Figure 5A) on a yellow green-colored paper are developed using the magnetically active PCDA. In contrast, second level structures can be clearly observed in the fluorescence microscopic image (Figure 5E). When the background color of the fingermark deposited substrate is red, one cannot take advantage of the fluorescence emission property of the heat-treated PDA (Figure 6). However, the blue-colored PDA formed initially by UVirradiation can be readily observed optically. As can be seen by inspection of Figure 6A, heat treatment of the blue-colored latent image on a red substrate causes the latent fingerprint to become invisible. Although the latent fingerprint is difficult to visualize optically as well as by using a fluorescence microscope both before or after heat treatment of the magnetically active PCDA-coated image (Figure 6B,D,E), the distinctive bluecolored PDA generated by using UV irradiation enables ready distinction of second level structures from the red-colored background (Figure 6C).

Figure 5. (A) Photographs of a latent fingerprint developed with PCDA−MNP composite on yellow green-colored paper (left), upon UV irradiation (254 nm, 1 mW/cm2, 10 s) (middle), and after subsequent heat treatment (80 °C, 20 s) (right). (B−D) Optical microscopic images of the latent fingermark developed with PCDA− MNP particles as coated (B), after UV irradiation (C), and after subsequent heat treatment (D). (E) Fluorescence microscopic image of the latent fingermark obtained after heat treatment of the PDA− MNP coated fingermark.

Both optical and fluorescence methods can be utilized to image latent fingermarks when the color of the substrate on which the fingerprint is deposited is black. As can be seen by inspection of Figure 7A, before UV irradiation, the magnetically active PCDA immobilized on the latent fingerprint appears as an off-white colored image (Figure 7A, left). The image becomes nearly invisible following both irradiation and subsequent heat treatment (Figure 7A, center and right). The monomer-treated latent image can be visualized using an D


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Figure 6. (A) Photographs of a latent fingerprint developed with PCDA−MNP composite on red-colored paper (left), upon UV irradiation (254 nm, 1 mW/cm2, 10 s) (middle), and after subsequent heat treatment (80 °C, 20 s) (right). (B−D) Optical microscopic images of the latent fingermark developed with PCDA−MNP particles as coated (B), after UV irradiation (C), and after subsequent heat treatment (D). (E) Fluorescence microscopic image of the latent fingermark obtained after heat treatment of the PDA−MNP coated fingermark.

Figure 7. (A) Photographs of a latent fingerprint developed with PCDA−MNP composite on a black-colored paper (left), upon UV irradiation (254 nm, 1 mW/cm2, 10 s) (middle), and after subsequent heat treatment (80 °C, 20 s) (right). (B−D) Optical microscopic images of the latent fingermark developed with PCDA−MNP particles as coated (B), after UV irradiation (C), and after subsequent heat treatment (D). (E) Fluorescence microscopic image of the latent fingermark obtained after heat treatment of the PDA−MNP coated fingermark.

optical microscope (Figure 7B,C) and the heat-treated polymerized PDA latent image is clearly observable using a fluorescence microscope (Figure 7C). The results show that the three distinctive colors of the latent image associated with the DA monomeric state (pale brown), PDA state generated by UV irradiation (blue), and subsequent heat treatment (red) can be used to analyze a fingerprint. Moreover, the multiple colors possible for visualization of a single latent fingerprint serves as a unique advantage of the newly developed method in comparison to conventional dusting powder approaches, which often provide only one color per application. Moreover, reasonably good ridge patterns, including level 2 features, can be observed using the new technique independent of the background color of the substrate. Finally, the red-colored fluorescence emission arising from the heat-treated PDA enables clear observation of latent fingermarks on solid substrates having various background colors.

consequence of the fact that the powders align along ridge patterns of the fingerprints when a magnetic field is applied. In addition, the monomeric diacetylene undergoes a pale brownto-blue color change upon UV irradiation and subsequent heat treatment of the fingerprint image creates a red-colored and fluorescent image. When combined, the pale brown, blue, and red colors along with the red fluorescence enable efficient visualization of latent fingerprints marked on papers having different background colors.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.6b00566.

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CONCLUSIONS The study described above led to the development of magnetically responsive diacetylene powders that can be utilized for latent fingerprint imaging. Addition of magnetic nanoparticles to appropriate diacetylene monomers produces powders that have unique advantages associated with their inherent magnetic properties as well as colorimetric responses. By using the new approach, sebaceous latent fingerprints deposited on solid substrates are readily visualized as a

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Optical and fluorescence microscopic images of a PCDAcoated latent fingerprint (PDF)

AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (J.-M.K.). *E-mail: [email protected] (C.W.L.). Notes

The authors declare no competing financial interest. E


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ACKNOWLEDGMENTS This investigation was supported financially by the National Research Foundation of Korea (NRF) grant funded by the Korean Government (MSIP) (No. 2014R1A2A1A01005862).

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A Magnetically Responsive Polydiacetylene Precursor for Latent

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