Next Article in Journal
Recent Developments in Inonotus obliquus (Chaga mushroom) Polysaccharides: Isolation, Structural Characteristics, Biological Activities and Application
Previous Article in Journal
Degradation of Styrenic Plastics during Recycling: Accommodation of PP within ABS after WEEE Plastics Imperfect Sorting
Previous Article in Special Issue
Synthesis of an Addition-Crosslinkable, Silicon-Modified Polyolefin via Reactive Extrusion Monitored by In-Line Raman Spectroscopy
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
Journals
Polymers
Volume 13
Issue 9
10.3390/polym13091438
polymers-logo
Submit to this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share announcement Help format_quote Cite question_answer Discuss in SciProfiles thumb_up
...
Endorse textsms
...
Comment
first_page
settings
Order Article Reprints
Font Type:
Arial Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Width:
Background:
Article

Chemical Imaging of Single Anisotropic Polystyrene/Poly (Methacrylate) Microspheres with Complex Hierarchical Architecture

by
Alexandra Wagner
1,
Stefanie Wagner
2,
Jan-Erik Bredfeldt
1,
Julia C. Steinbach
1,
Ashutosh Mukherjee
1,3,
Sandra Kronenberger
2,
Kai Braun
3,
Andreas Kandelbauer
1,
Hermann A. Mayer
2 and
Marc Brecht
1,*
1
Process Analysis and Technology (PA&T), Reutlingen Research Institute, Reutlingen University, Alteburgstrasse 150, 72762 Reutlingen, Germany
2
Institute of Inorganic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
3
Institute of Physical Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
*
Author to whom correspondence should be addressed.
Polymers 2021, 13(9), 1438; https://doi.org/10.3390/polym13091438
Submission received: 25 March 2021 / Revised: 23 April 2021 / Accepted: 26 April 2021 / Published: 29 April 2021
(This article belongs to the Special Issue Silicon-Containing Polymers)
Browse Figures
Versions Notes

Abstract

:
Monodisperse polystyrene spheres are functional materials with interesting properties, such as high cohesion strength, strong adsorptivity, and surface reactivity. They have shown a high application value in biomedicine, information engineering, chromatographic fillers, supercapacitor electrode materials, and other fields. To fully understand and tailor particle synthesis, the methods for characterization of their complex 3D morphological features need to be further explored. Here we present a chemical imaging study based on three-dimensional confocal Raman microscopy (3D-CRM), scanning electron microscopy (SEM), focused ion beam (FIB), diffuse reflectance infrared Fourier transform (DRIFT), and nuclear magnetic resonance (NMR) spectroscopy for individual porous swollen polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles. Polystyrene particles were synthesized with different co-existing chemical entities, which could be identified and assigned to distinct regions of the same particle. The porosity was studied by a combination of SEM and FIB. Images of milled particles indicated a comparable porosity on the surface and in the bulk. The combination of standard analytical techniques such as DRIFT and NMR spectroscopies yielded new insights into the inner structure and chemical composition of these particles. This knowledge supports the further development of particle synthesis and the design of new strategies to prepare particles with complex hierarchical architectures.

1. Introduction

Modified polystyrene particles are versatile and popular in many scientific fields, e.g., in material sciences, engineering, catalysis, nanomedicine, and biotechnology [1,2,3,4]. The tailored design of particles enables new approaches for imaging and drug delivery [5]. One of the most important approaches is the tuning of particle morphology and topology as well as their charge distribution [4]. The most prominent examples are Janus particles, which are special types of nanoparticles or microparticles whose surfaces have regions of two or more distinctly different physical properties. This unique surface of Janus particles allows different types of chemistry to co-exist on the same particle [6].
The availability of synthetic procedures leading to polystyrene spheres with narrow size distributions and their ability to swell in different media make them ideal templates for the generation of more complex isotropic and anisotropic materials [6,7,8,9,10,11,12,13,14,15]. For this purpose, it is important to control specific particle properties, such as size and size distribution, shape, surface porosity, and chemical composition during synthesis [11].
SEM and bulk-IR as well as solid-state NMR spectroscopy have proven to be the most efficient characterization methods for these particles [16,17,18,19,20,21,22,23,24,25]. The high magnification of SEM images enables precise characterization of their size, shape, and surface properties. Additionally, the combination of SEM and milling with a focused ion beam (FIB) allows insight into their internal structure. However, with these techniques, it is not possible to obtain information about the distribution of chemical components and functionalities across these particles.
The high-resolution imaging technique, 3D confocal Raman microscopy (3D-CRM), is often used in combination with other analytical methods to characterize the chemical and molecular compositions of materials. The correlation of Raman imaging and SEM (RISE), especially, provides information on physical surface properties in combination with molecular compound information of a sample [26,27]. Depth profiles and 3D images can be created with exceptionally good spectral and spatial resolution [28], and the chemical properties can be analyzed with high spatial resolution close to the diffraction limit of light. The 3D-CRM technique is non-invasive, non-destructive, and does not require any complex sample preparation such as staining or labeling [29,30,31,32,33,34]. Since no interference with vibrational bands from water is observed, the particles can be examined directly from aqueous solution.
Here, we present a micro-spectroscopic analysis for the characterization of anisotropic single polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles. The correlation of the results from DRIFT, NMR, SEM, and 3D-CRM enables us to show that particles with Janus-like properties are formed. Using this combination of methods allowed us to observe changes in the particle properties in response to variations in reaction conditions applied during synthesis.

2. Materials and Methods

2.1. Particle Synthesis

Glycidyl methacrylate (GMA), benzoyl peroxide (BPO), and sodium dodecyl sulfate (SDS) were purchased from abcr GmbH, Karlsruhe, Germany. Ethylene di-methacrylate (EDMA) was obtained from Sigma-Aldrich, Taufkirchen, Germany. Polyvinylpyrrolidone (PVP) and 1-hexanol were supplied from Merck GmbH, Darmstadt, Germany.
We sonicated 1 g of polystyrene and 30 mL of deionized water for 5 min. The suspension was stirred (200 rpm) for 1.5 h at 30 °C and argon was bubbled through the solution. An emulsion of GMA (7 mL), EDMA (7 mL), SDS (0.3 g), PVP (3 g) 25,000 D, 1-hexanol, 0.56 g BPO, and 250 mL of water was prepared by sonicating the mixture (10 min), stirring at RT for 10 min, and bubbling argon through the solution for another 10 min. The emulsion was added to the suspension of the polystyrene particles and stirred for 2 h at 30 °C. The temperature was raised to 70 °C and kept constant for 24 h. The particles were separated and washed with water (3 times) and ethanol (3 times) and dried at 70 °C for 30 min. The volume of 1-hexanol was increased from 7 mL (S2) by 14 mL (S3) to 21 mL (S4).

2.2. Particle Characterization

A Hitachi SU8030 (Hitachi High-Technologies Corporation, Tübingen, Germany) was used to obtain SEM images. FIB cuts were prepared with a dual cross-beam FEI Strata DB235 (FEI, Tübingen, Germany). The primary Ga+ Ion current was reduced to 50 pA via an aperture. DRIFT spectra were measured with a Bruker Vertex 70 spectrometer (Bruker, Ettlingen, Germany). Solid-state NMR spectra were recorded on a Bruker Avance III-HD spectrometer (Bruker, Ettlingen, Germany) with a wide-bore magnet operating at 300.13 MHz (1H) and 75.46 MHz (13C). The powdered samples of the respective materials were packed in 4 mm o.d. zirconia rotors; the spinning speed was 10 KHz, the relaxation delay 4 s, and the contact time 2 ms.
For Raman measurements, particle samples were dispersed in ethanol and thoroughly mixed. One droplet (10 µL) of the mixed dispersion was placed on a cleansed sapphire microscope slide and evaporated. Raman spectra and Raman images were obtained using a confocal Raman microscope (WiTec alpha300 RA&S, Ulm, Germany) equipped with an air objective (EC Epiplan-Neofluar DIC M27, 100×, NA = 0.9, Carl Zeiss, Oberkochen, Germany) with a lateral resolution of 360 nm. This system was equipped with a lens-based UHTS 300 spectrometer (WiTec, Ulm, Germany) connected via a 100 µm (NA = 0.12) multi-mode optical fiber and thermoelectric cooled CCD and EMCCD (DU970N-BV, WiTec, Ulm, Germany). All Raman experiments were carried out using a laser of 532 nm with a nominal output power of approx. 39 mW and a grating of 600 lines/mm. Data were processed using Control 5.0 software provided by WITec. All experiments were carried out in ambient conditions. We chose sapphire as a substrate due to its low background signal, which does not interfere with the signal intensity from the region of interest. Additionally, the absorbance signals of sapphire do not overlap with those of the sample, making it an ideal substrate for Raman analysis of these particles.

3. Results

Polystyrene particles (S1) were synthesized from styrene via a free-radical chain propagation polymerization. Porous poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles S2, S3, and S4 were prepared in a seeded swelling polymerization process. In this process, polystyrene particles S1 were dispersed in water and treated with an emulsion consisting of glycidyl methacrylate (GMA), ethylene di-methacrylate (EDMA), sodium lauryl sulfate (SDS), polyvinyl pyrrolidone (PVP), and 1-hexanol. Benzoyl peroxide was added to start the polymerization. To control the size of the pores, the amount of the porogen (1-hexanol) was gradually increased from 7 mL (S2) by 14 mL (S3) to 21 mL (S4) under otherwise identical reaction conditions.
Figure 1A shows the solid-state 13C CP/MAS NMR spectra of the particles S1–S4. In the spectra of S1, characteristic bands of polystyrene are observed, whereas the spectra of S2–S4 show the characteristic peaks of poly (glycidyl methacrylate-co-ethylene di-methacrylate) polymers as well as those of polystyrene.
The carbon nuclei forming the polymer backbone resonate at 18, 44, and 54 ppm; the oxygen-containing side chains resonate at 63 and 66 ppm, whereas the carbonyl carbon atoms produce to a broad peak at 176 ppm. All samples still contained a considerable amount of polystyrene as indicated by broad peaks in the aromatic region at 127 and 145 ppm. This finding is supported by the comparison of the DRIFT spectrum of polystyrene (S1) with those of the particles S2–S4 shown in Figure 1B. All DRIFT spectra of the materials S2–S4 contain absorption bands that are assigned to aromatic C=C at 1600 cm−1, C=C–H bending at 700 cm−1 and 735 cm−1, as well as C=C–H stretching at 3023–3083 cm−1. These vibrations of the polystyrene appear along with the characteristic absorptions of poly (glycidyl methacrylate-co-ethylene di-methacrylate) polymers [35]. Characteristic for that polymer is the ester carbonyl (C=O) stretch at around 1725 cm−1 and the aliphatic C–H stretch just around 2980 cm−1.
The surface/bulk porosity, roughness, and chemical distribution were revealed by SEM and 3D-CRM. Figure 2 compares the images of the samples S1–S4 generated by SEM (left column A,C,E,G,I) with those obtained by 3D-CRM (right column B,D,F,H,J). For S1, both techniques revealed spherical, highly monodisperse particles. After the swelling of the polystyrene particles S1 with EDMA, GMA, and 1-hexanol (porogen), larger particles were found with smaller particles attached to them (Figure 2C,E,G,I). The small particles had a more or less spherical shape and a smooth surface; the large particles were dented at one side and are porous. With an increasing amount of porogen, which was in the series S2 (7 mL), S3 (14 mL), and S4 (21 mL), the pore size increased. In the cases of S2 and S3, the small spherical particles were located in the dented area of the large particles (Figure 2C,E,G). Interestingly, the particles S4 showed non-porous caps in the area of the dent (Figure 2I). To reveal the porosity of the bulk, particles from S3 were cut through by line milling with a Ga+ FIB (50 pA beam current). The corresponding SEM images (Figure 2K,L) demonstrate that the porosity inside the main particle is comparable to that on its surface.
The 3D-CRM images of the samples S1–S4 shown in Figure 2B,D,F,H,J reproduced the size and the shape of the particles as shown in the corresponding SEM images. Due to the poor resolution of the optical light-microscopy compared with SEM, the porosity and surface morphology can only be assumed. However, the advantage of 3D-CRM is that the chemical composition and distribution of the sample can be deduced by the fingerprint Raman spectrum at different positions on the particles.
The assignment of the Raman peaks to specific vibration bands and the resulting color coding of the images are shown in Figure 3. Figure 3A shows a two-dimensional scan of one particle. Here, the integral intensity of Raman scattering in the range of 350–3200 cm−1 is used. The particle is distinguishable from the background. In the region of the attached small particle, the observed intensity is significantly higher compared with the main particle. Figure 3B,C shows Raman spectra recorded at the positions marked by X. The Raman spectrum recorded at the position of the small particle can be assigned to polystyrene due to the characteristic Raman peaks at 1002, 1603, and 1448 cm−1 (red arrows) [35,36,37]. The Raman spectrum recorded at the main particle can be assigned to poly (glycidyl methacrylate-co-ethylene di-methacrylate) polymer due to the Raman peak at 1723 cm−1 [35]. The peaks at 1454 and 1259 cm−1 (blue arrows) can be assigned to ketones and epoxides from EDMA and GMA, respectively [35,38,39].
A principal component analysis (PCA) of all Raman spectra yielded two principal components explaining 95% of the total data. Based on this number of relevant components, the data were analyzed with Control 5.0 data processing software provided by WITec using an inbuilt PCA. The components were assigned to colors (blue, red) for better visualization. Regions dominated by the polystyrene were assigned the color red, while those dominated by EDMA/GMA were assigned the color blue; the resulting image is depicted in Figure 3D. Consequently, the small particles attached to the larger particles could be assigned to polystyrene and the large particles to EDMA/GMA. Based on this assignment, all 3D-CRM images in Figure 2 are color-coded following the same procedure.

4. Discussion

A correlation between NMR, DRIFT, SEM, and 3D-CRM is presented in this study of polystyrene particles. With the combination of these techniques, the swelling of polystyrene/poly (glycidyl methacrylate-co-ethylene di-methacrylate) particles depending on the concentration of the porogen (1-hexanol) was studied. The 13C CP/MAS NMR spectra (Figure 1A) show that, in all swollen particles, polystyrene and poly (glycidyl methacrylate-co-ethylene di-methacrylate) are present. These results are consistent with the results of the DRIFT measurements (Figure 1B).
The first indications of a deviation from uniformity/sphericity of the particles are found in the SEM images (Figure 2). The SEM images of the particles from the synthesis using 7 mL (S2) (Figure 2C) and 14 mL (S3) (Figure 2E) porogen show different types of particles. They clearly show small- and large-sized particles. The large particles show a dented area where the small particles are attached. The relative amount of small particles in relation to the larger ones varies within the sample. SEM revealed that the surface roughness of the small particles is lower than that of the large particles. When 21 mL (S4) (Figure 2I) of porogen was used, no dented areas or small particles were observed. The S4 particles were almost spherical, with a flat nonporous cap in the region wherein the dented areas in the other particles were observed. This reduced roughness is comparable to the roughness that was found for small particles (S2 and S3) at lower porogen concentrations.
The porosity of the particles on the surface and in the bulk was further investigated. For this, the particles were milled with FIB. SEM images of a milled particle S3 (14 mL porogen) are shown in Figure 2K,L. The FIB image indicates a comparable porosity throughout the particle. Milling of the smaller particles was unsuccessful.
Next, the chemical composition of individual particles was studied in detail with 3D-CRM. The analysis of the Raman spectra enables an assignment of the observed vibrational bands to molecule specific vibrations. The spectra recorded at the position of the small particles are dominated by vibrations assigned to polystyrene, whereas the spectra recorded at the large particles show bands assigned to poly (glycidyl methacrylate-co-ethylene di-methacrylate). The CRM images suggest that polystyrene is extruded from the forming EDMA/GMA polymer network during polymerization. When the porogen concentration was increased to 21 mL (S4) (Figure 2I,J), the extrusion of polystyrene remained incomplete, and the extruded polystyrene formed an adherent cap on the dented areas of the large particles.
A presumed mechanism for the formation of these particles is shown in Scheme 1.
Pore formation in particles depends on the solubility of porogen and the seed particle. Materials with similar solubility parameters have a high affinity to each other. Notably, 1-hexanol has a poor theoretical solubility with polystyrene and poly (glycidyl methacrylate-co-ethylene di-methacrylate). As polymerization starts, phase separation occurs due to insufficient solubility and 1-hexanol is displaced as an inert molecule, leaving the pore structure in the particle. In the magnified SEM image (Figure 2G), it appears that polystyrene is squeezed out of the particle. This can be also explained by solubility effects. Due to a rather good solubility in GMA and EDMA, the polystyrene bead is dissolved into individual polymer chains of high mobility and flexibility [40,41,42]. Upon GMA and EDMA polymerization, phase separation occurs again, and polystyrene becomes insoluble in the three-dimensional network and is squeezed out.
The syntheses described here yield particles with variable size, shape, and porosity. This is achieved by changing only one parameter, which is the amount of porogen added during synthesis. In chemistry, managing critical parameters precisely plays a crucial role in the final properties of the particles [11]. The 3D-CRM results revealed that these particles show a Janus particle behavior not only in terms of their morphology, but also in terms of their chemical composition. Both properties are controllable by the concentration of the porogen. We also showed that 3D-CRM is a useful tool for analyzing and characterizing inhomogeneous particles in a spatially resolved and three-dimensional way. Thus, the synthesis can be adjusted accordingly to achieve particles of defined 3D morphology and controlled chemical composition. Potential applications of these particles include as template molecules for large porous silica microspheres for protein separation, drug delivery systems, microcapsule systems for extrinsic self-healing applications, or, for instance, as templating materials used in energy storage applications [18,43,44,45,46,47,48,49,50,51].

5. Conclusions

This study shows that the combination of NMR, DRIFT, SEM, and 3D-CRM is well-suited for controlled synthesis of polymer particles. Synthesized particles with varying proportions of porogen were analyzed with the aforementioned methods at each step of synthesis development. This provides direct insight into the development of the synthesis at every step. Both solid-state 13C CP/MAS NMR and DRIFT spectra showed that all particles (S1, S2, S3, and S4) contain a significant amount of polystyrene. Swollen particles (S2, S3 and S4) showed both polystyrene and other constituent byproducts as a result of synthesis. Interpretation of the morphology and the chemical composition of the particles was facilitated by the combined use of SEM and 3D-CRM. This approach revealed the distribution of the chemical entities across the particles. We found that 3D-CRM is indispensable for the assignment of the different chemical entities to the morphological features on the particles, and distribution of chemical species can be visualized using PCA. Similar problems are often analyzed with fluorescence microscopy; however, this requires the addition of staining chemicals or labeling steps [29,30,31]. For the selection of appropriate labels, making assumptions about the resulting particles is necessary. Consequently, the selection of the labels influences the information accessible by the measurement and may bias the result. In contrast, the marker-free approach presented here minimizes sample alteration and eliminates the need for an additional step, since no labeling is necessary for 3D-CRM measurements and the Raman spectra provide a detailed insight into the chemical composition.

Author Contributions

Conceptualization, H.A.M. and M.B.; Data curation, A.W. and J.-E.B.; Formal analysis, A.W., S.W. and J.-E.B.; Funding acquisition, H.A.M. and M.B.; Methodology, A.W., S.W., J.-E.B., K.B. and A.K.; Project administration, S.K., H.A.M. and M.B.; Software, A.W. and J.-E.B.; Supervision, A.K., H.A.M. and M.B.; Visualization, A.W., S.W., J.-E.B. and Kai Braun; Writing—original draft, A.W., A.K., H.A.M. and M.B.; Writing—review & editing, J.C.S., A.M., A.K., H.A.M. and M.B. All authors have read and agreed to the published version of the manuscript.

Funding

This work was supported by the Bundesministerium für Wirtschaft und Energie (AiF/ZIM, ZF4019203SL8). A.M. would like to acknowledge the financial support within the framework IngenieurNachwuchs 2016 (project: CompeTERS) by the German Federal Ministry of Education and Research (BMBF). J.C.S. was funded by German Federal Ministry of Education and Research, funding program Forschung an Fachhochschulen (project 13FH647IX6). SEM/EDX measurements on a Hitachi SU 8030 SEM were supported by the DFG under contract INST 37/829-1 FUGG. The article processing charge was funded by the Baden−Württemberg Ministry of Science, Research and Culture in the funding program Open Access Publishing.

Institutional Review Board Statement

Not applicable.

Informed Consent Statement

Not applicable.

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Acknowledgments

The authors are grateful to Elke Nadler (University of Tübingen) for performing SEM measurements.

Conflicts of Interest

The authors declare no conflict of interest. The funders had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript; or in the decision to publish the results.

References

  1. Gulka, C.P.; Swartz, J.D.; Trantum, J.R.; Davis, K.M.; Peak, C.M.; Denton, A.J.; Haselton, F.R.; Wright, D.W. Coffee rings as low-resource diagnostics: Detection of the malaria biomarker Plasmodium falciparum histidine-rich protein-II using a surface-coupled ring of Ni(II)NTA gold-plated polystyrene particles. ACS Appl. Mater. Interfaces 2014, 6, 6257–6263. [Google Scholar] [CrossRef] [PubMed]
  2. Grafmueller, S.; Manser, P.; Diener, L.; Diener, P.-A.; Maeder-Althaus, X.; Maurizi, L.; Jochum, W.; Krug, H.F.; Buerki-Thurnherr, T.; von Mandach, U.; et al. Bidirectional Transfer Study of Polystyrene Nanoparticles across the Placental Barrier in an ex Vivo Human Placental Perfusion Model. Environ. Health Perspect. 2015, 123, 1280–1286. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  3. Holzapfel, V.; Musyanovych, A.; Landfester, K.; Lorenz, M.R.; Mailänder, V. Preparation of Fluorescent Carboxyl and Amino Functionalized Polystyrene Particles by Miniemulsion Polymerization as Markers for Cells. Macromol. Chem. Phys. 2005, 206, 2440–2449. [Google Scholar] [CrossRef]
  4. Fröhlich, E. The role of surface charge in cellular uptake and cytotoxicity of medical nanoparticles. Int. J. Nanomed. 2012, 7, 5577–5591. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  5. Choi, J.; Xue, Y.; Xia, W.; Ray, T.R.; Reeder, J.T.; Bandodkar, A.J.; Kang, D.; Xu, S.; Huang, Y.; Rogers, J.A. Soft, skin-mounted microfluidic systems for measuring secretory fluidic pressures generated at the surface of the skin by eccrine sweat glands. Lab Chip 2017, 17, 2572–2580. [Google Scholar] [CrossRef] [PubMed]
  6. Fan, J.-B.; Song, Y.; Liu, H.; Lu, Z.; Zhang, F.; Liu, H.; Meng, J.; Gu, L.; Wang, S.; Jiang, L. A general strategy to synthesize chemically and topologically anisotropic Janus particles. Sci. Adv. 2017, 3, e1603203. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  7. Yang, M.; Cao, L.; Tan, L. Synthesis of sea urchin-like polystyrene/polyaniline microspheres by seeded swelling polymerization and their catalytic application. Colloids Surf. A Physicochem. Eng. Asp. 2014, 441, 678–684. [Google Scholar] [CrossRef]
  8. Shim, S.-E.; Cha, Y.-J.; Byun, J.-M.; Choe, S. Size control of polystyrene beads by multistage seeded emulsion polymerization. J. Appl. Polym. Sci. 1999, 71, 2259–2269. [Google Scholar] [CrossRef]
  9. Zhang, Y.; Lu, Y.; Zhong, J.; Li, W.; Wei, Q.; Wang, K. Molecularly imprinted polymer microspheres prepared via the two-step swelling polymerization for the separation of lincomycin. J. Appl. Polym. Sci. 2019, 136, 47938. [Google Scholar] [CrossRef]
  10. Li, Y.; Wang, Z.; Wang, C.; Zhao, Z.; Xue, G. Controlling the morphology of micrometre-size polystyrene/polyaniline composite particles by Swelling–Diffusion–Interfacial-Polymerization Method. Polymer 2011, 52, 409–414. [Google Scholar] [CrossRef]
  11. Park, S.H.; Kim, J.; Lee, W.-E.; Byun, D.-J.; Kim, M.H. One-Step Synthesis of Hollow Dimpled Polystyrene Microparticles by Dispersion Polymerization. Langmuir 2017, 33, 2275–2282. [Google Scholar] [CrossRef]
  12. Omer-Mizrahi, M.; Margel, S. Synthesis and characterization of spherical and hemispherical polyepoxide micrometer-sized particles of narrow size distribution by a single-step swelling of uniform polystyrene template microspheres with glycidyl methacrylate. J. Polym. Sci. A Polym. Chem. 2007, 45, 4612–4622. [Google Scholar] [CrossRef]
  13. Galperin, A.; Margel, S. Synthesis and characterization of new micrometer-sized radiopaque polymeric particles of narrow size distribution by a single-step swelling of uniform polystyrene template microspheres for X-ray imaging applications. Biomacromolecules 2006, 7, 2650–2660. [Google Scholar] [CrossRef]
  14. Boguslavsky, L.; Margel, S. Synthesis and characterization of micrometer-sized homo and composite polyacrylonitrile particles of narrow size distribution on the basis of single-step swelling of uniform polystyrene template microspheres. J. Polym. Sci. A Polym. Chem. 2004, 42, 4847–4861. [Google Scholar] [CrossRef]
  15. Bryce, D.A.; Kitt, J.P.; Harris, J.M. Confocal Raman Microscopy Investigation of Molecular Transport into Individual Chromatographic Silica Particles. Anal. Chem. 2017, 89, 2755–2763. [Google Scholar] [CrossRef]
  16. Wang, W.-P.; Pan, C.-Y. Preparation and characterization of polystyrene/graphite composite prepared by cationic grafting polymerization. Polymer 2004, 45, 3987–3995. [Google Scholar] [CrossRef]
  17. Podsiadlo, P.; Stachowiak, G.W. Characterization of surface topography of wear particles by SEM stereoscopy. Wear 1997, 206, 39–52. [Google Scholar] [CrossRef]
  18. Wang, Q.; Zhang, Y.; Jiang, H.; Li, X.; Cheng, Y.; Meng, C. Designed mesoporous hollow sphere architecture metal (Mn, Co, Ni) silicate: A potential electrode material for flexible all solid-state asymmetric supercapacitor. Chem. Eng. J. 2019, 362, 818–829. [Google Scholar] [CrossRef]
  19. Chatterjee, J.; Haik, Y.; Chen, C.-J. Modification and characterization of polystyrene-based magnetic microspheres and comparison with albumin-based magnetic microspheres. J. Magn. Magn. Mater. 2001, 225, 21–29. [Google Scholar] [CrossRef]
  20. Nagy, J.B. Multinuclear NMR characterization of microemulsions: Preparation of monodisperse colloidal metal boride particles. Colloids Surf. 1989, 35, 201–220. [Google Scholar] [CrossRef]
  21. Leu, G.; Liu, Y.; Werstler, D.D.; Cory, D.G. NMR Characterization of Elastomer−Carbon Black Interactions. Macromolecules 2004, 37, 6883–6891. [Google Scholar] [CrossRef]
  22. Stinner, C.; Tang, Z.; Haouas, M.; Weber, T.; Prins, R. Preparation and 31P NMR Characterization of Nickel Phosphides on Silica. J. Catal. 2002, 208, 456–466. [Google Scholar] [CrossRef]
  23. Santamaria, A.; Mondragon, F.; Molina, A.; Marsh, N.; Eddings, E.; Sarforim, A. FT-IR and 1H NMR characterization of the products of an ethylene inverse diffusion flame. Combust. Flame 2006, 146, 52–62. [Google Scholar] [CrossRef]
  24. Joshi, R.; Feldmann, V.; Koestner, W.; Detje, C.; Gottschalk, S.; Mayer, H.A.; Sauer, M.G.; Engelmann, J. Multifunctional silica nanoparticles for optical and magnetic resonance imaging. Biol. Chem. 2013, 394, 125–135. [Google Scholar] [CrossRef]
  25. Lica, G.C.; Zelakiewicz, B.S.; Tong, Y.Y. Electrochemical and NMR characterization of octanethiol-protected Au nanoparticles. J. Electroanal. Chem. 2003, 554–555, 127–132. [Google Scholar] [CrossRef]
  26. Markervich, E.; Salitra, G.; Levi, M.D.; Aurbach, D. Capacity fading of lithiated graphite electrodes studied by a combination of electroanalytical methods, Raman spectroscopy and SEM. J. Power Sources 2005, 146, 146–150. [Google Scholar] [CrossRef]
  27. Santini, A.; Miletic, V. Comparison of the hybrid layer formed by Silorane adhesive, one-step self-etch and etch and rinse systems using confocal micro-Raman spectroscopy and SEM. J. Dent. 2008, 36, 683–691. [Google Scholar] [CrossRef]
  28. Jin, Q.; Li, M.; Polat, B.; Paidi, S.K.; Dai, A.; Zhang, A.; Pagaduan, J.V.; Barman, I.; Gracias, D.H. Mechanical Trap Surface-Enhanced Raman Spectroscopy for Three-Dimensional Surface Molecular Imaging of Single Live Cells. Angew. Chem. 2017, 129, 3880–3884. [Google Scholar] [CrossRef]
  29. Liu, B.; Möhwald, H.; Wang, D. Synthesis of Janus particles via kinetic control of phase separation in emulsion droplets. Chem. Commun. 2013, 49, 9746–9748. [Google Scholar] [CrossRef]
  30. Chang, F.; Ouhajji, S.; Townsend, A.; Sanogo Lacina, K.; van Ravensteijn, B.G.P.; Kegel, W.K. Controllable synthesis of patchy particles with tunable geometry and orthogonal chemistry. J. Colloid Interface Sci. 2021, 582, 333–341. [Google Scholar] [CrossRef]
  31. Maisch, J.; Jafarli, F.; Chassé, T.; Blendinger, F.; Konrad, A.; Metzger, M.; Meixner, A.J.; Brecht, M.; Dähne, L.; Mayer, H.A. One-pot synthesis of micron partly hollow anisotropic dumbbell shaped silica core-shell particles. Chem. Commun. 2016, 52, 14392–14395. [Google Scholar] [CrossRef] [PubMed]
  32. Bhaskar, S.; Gibson, C.T.; Yoshida, M.; Nandivada, H.; Deng, X.; Voelcker, N.H.; Lahann, J. Engineering, characterization and directional self-assembly of anisotropically modified nanocolloids. Small 2011, 7, 812–819. [Google Scholar] [CrossRef] [PubMed]
  33. Kumamoto, Y.; Harada, Y.; Takamatsu, T.; Tanaka, H. Label-free Molecular Imaging and Analysis by Raman Spectroscopy. Acta Histochem. Cytochem. 2018, 51, 101–110. [Google Scholar] [CrossRef] [PubMed] [Green Version]
  34. Xie, W.; Walkenfort, B.; Schlücker, S. Label-free SERS monitoring of chemical reactions catalyzed by small gold nanoparticles using 3D plasmonic superstructures. J. Am. Chem. Soc. 2013, 135, 1657–1660. [Google Scholar] [CrossRef]
  35. Socrates, G. Polymers—Macromolecules. In Infrared and Raman Characteristic Group Frequencies: Tables and Charts, 3rd ed.; John Wiley & Sons LTD: Chichester, UK, 2015; ISBN 0470093072. [Google Scholar]
  36. Anema, J.R.; Brolo, A.G.; Felten, A.; Bittencourt, C. Surface-enhanced Raman scattering from polystyrene on gold clusters. J. Raman Spectrosc. 2010, 41, 745–751. [Google Scholar] [CrossRef]
  37. Palm, A. Raman Spectrum of Polystyrene. J. Phys. Chem. 1951, 55, 1320–1324. [Google Scholar] [CrossRef]
  38. Filipecka, K.; Miedziński, R.; Sitarz, M.; Filipecki, J.; Makowska-Janusik, M. Optical and vibrational properties of phosphorylcholine-based contact lenses-Experimental and theoretical investigations. Spectrochim. Acta A Mol. Biomol. Spectrosc. 2017, 176, 83–90. [Google Scholar] [CrossRef]
  39. Boerio, F.J.; Yuann, J.K. Determination of copolymer composition by Raman spectroscopy. J. Polym. Sci. Polym. Phys. Ed. 1973, 11, 1841–1848. [Google Scholar] [CrossRef]
  40. Gokmen, M.T.; Du Prez, F.E. Porous polymer particles—A comprehensive guide to synthesis, characterization, functionalization and applications. Prog. Polym. Sci. 2012, 37, 365–405. [Google Scholar] [CrossRef] [Green Version]
  41. Gong, B.-L.; Ke, C.-Y.; Geng, X.-D. Synthesis of Monodisperse Poly(glycidylmethacrylate-co-ethylene dimethacrylate) Beads and Their Application in Separation of Biopolymers. Chin. J. Chem. 2004, 22, 283–289. [Google Scholar] [CrossRef]
  42. Gong, B.; Ke, C.; Geng, X. Preparation of weak cation exchange packings based on monodisperse poly(glycidyl methacrylate-co-ethylene dimethacrylate) beads and their chromatographic properties. Anal. Bioanal. Chem. 2003, 375, 769–774. [Google Scholar] [CrossRef]
  43. Kutuzova, L.; Kandelbauer, A. Self-healing thermosets. In Handbook of Thermoset Plastics, 4th ed.; Dodiuk, H., Ed.; William Andrew Inc. & Elsevier: Norwich, NY, USA, 2021; ISBN 978-0-12-821632-3. [Google Scholar]
  44. Urdl, K.; Weiss, S.; Karpa, A.; Peric, M.; Zikulnig-Rusch, E.M.; Brecht, M.; Kandelbauer, A.; Müller, U.; Kern, W. Furan-functionalized melamine-formaldehyde particles performing Diels-Alder reactions. Eur. Polym. J. 2018, 108, 225–234. [Google Scholar] [CrossRef]
  45. Urdl, K.; Weiss, S.; Brodbeck, B.; Kandelbauer, A.; Zikulnig-Rusch, E.M.; Müller, U.; Kern, W. Homogeneous, monodispersed furan-melamine particles performing reversible binding and forming networks. Eur. Polym. J. 2019, 116, 158–168. [Google Scholar] [CrossRef]
  46. Urdl, K.; Kandelbauer, A.; Kern, W.; Müller, U.; Thebault, M.; Zikulnig-Rusch, E.M. Self-healing of densely crosslinked thermoset polymers—a critical review. Prog. Org. Coat. 2017, 104, 232–249. [Google Scholar] [CrossRef]
  47. Wang, Q.; Yang, H.; Meng, T.; Yang, J.; Huang, B.; Gu, F.L.; Zhang, S.; Meng, C.; Tong, Y. Boosting Electron Transfer with Heterointerface Effect for High-Performance Lithium-Ion Storage. Energy Storage Mater. 2021, 36, 365–375. [Google Scholar] [CrossRef]
  48. Wang, Q.; Li, Y.; Meng, T.; Huang, B.; Hu, L.; Su, H.; Meng, C.; Tong, Y. Engineering Heterostructure-Incorporated Metal Silicates Anchored on Carbon Nanotubes for Highly Durable Lithium Storage. ACS Appl. Energy Mater. 2021, 4, 1548–1559. [Google Scholar] [CrossRef]
  49. Meng, T.; Li, B.; Wang, Q.; Hao, J.; Huang, B.; Gu, F.L.; Xu, H.; Liu, P.; Tong, Y. Large-Scale Electric-Field Confined Silicon with Optimized Charge-Transfer Kinetics and Structural Stability for High-Rate Lithium-Ion Batteries. ACS Nano 2020, 14, 7066–7076. [Google Scholar] [CrossRef]
  50. Barbé, C.; Bartlett, J.; Kong, L.; Finnie, K.; Lin, H.Q.; Larkin, M.; Calleja, S.; Bush, A.; Calleja, G. Silica Particles: A Novel Drug-Delivery System. Adv. Mater. 2004, 16, 1959–1966. [Google Scholar] [CrossRef]
  51. Xia, H.; Wan, G.; Yang, F.; Wang, J.; Bai, Q. Preparation of monodisperse large-porous silica microspheres with polymer microspheres as the templates for protein separation. Mater. Lett. 2016, 180, 19–22. [Google Scholar] [CrossRef]
Polymers 13 01438 g001 550
Figure 1. (A) Solid-state 13C CP/MAS NMR spectra of particles S1–S4 and (B) DRIFT spectra of the particles S1–S4.
Figure 1. (A) Solid-state 13C CP/MAS NMR spectra of particles S1–S4 and (B) DRIFT spectra of the particles S1–S4.
Polymers 13 01438 g001
Polymers 13 01438 g002 550
Figure 2. Particles S1–S4 imaged by SEM (A,C,E,G,I) and the corresponding Raman images (B,D,F,H,J). A magnified SEM image of S3 (G) and the corresponding Raman image (H) are shown. A particle of the sample S3 milled with Ga+ FIB (K,L). Particles S1 (A,B) consist of pure polystyrene. Particles S2, S3, and S4 consist of poly (glycidyl methacrylate-co-ethylene di-methacrylate) polymer with an increasing concentration of porogen S2 (C,D; 7 mL porogen), S3 (E,F; 14 mL porogen), and S4 (I,J; 21 mL porogen).
Figure 2. Particles S1–S4 imaged by SEM (A,C,E,G,I) and the corresponding Raman images (B,D,F,H,J). A magnified SEM image of S3 (G) and the corresponding Raman image (H) are shown. A particle of the sample S3 milled with Ga+ FIB (K,L). Particles S1 (A,B) consist of pure polystyrene. Particles S2, S3, and S4 consist of poly (glycidyl methacrylate-co-ethylene di-methacrylate) polymer with an increasing concentration of porogen S2 (C,D; 7 mL porogen), S3 (E,F; 14 mL porogen), and S4 (I,J; 21 mL porogen).
Polymers 13 01438 g002
Polymers 13 01438 g003 550
Figure 3. (A) Raman intensity image of a particle S3. (B,C) Raman spectra recorded in the range from 500 to 3200 cm−1 at the locations marked with X. Characteristic Raman signals are marked with red and blue arrows (see text for details). (D) The Raman image is based on the assignment of spectra in each pixel. Pixels dominated by spectrum (B,C) are color-coded with red and blue, respectively.
Figure 3. (A) Raman intensity image of a particle S3. (B,C) Raman spectra recorded in the range from 500 to 3200 cm−1 at the locations marked with X. Characteristic Raman signals are marked with red and blue arrows (see text for details). (D) The Raman image is based on the assignment of spectra in each pixel. Pixels dominated by spectrum (B,C) are color-coded with red and blue, respectively.
Polymers 13 01438 g003
Polymers 13 01438 sch001 550
Scheme 1. (A,B) Suspension of monodisperse micron-sized polystyrene beads in water mixed with an emulsion consisting of GMA, EDMA, SDS, PVP, BPO, and 1-hexanol (in adequate quantities for S2, S3, and S4). For clarity, BPO (radical starter) is not included in the scheme. Hydrophobic attractions between PS and SDS are responsible for the formation of micelles. Water-soluble PVP stabilizes the micelles from the outside. (C) The particles swell due to the diffusion of GMA, EDMA, 1-hexanol, and BPO into the bead. (D) Upon polymerization, both methacrylates form the porous poly (glycidyl methacrylate-ethylene dimethacrylate) network with 1-hexanol as an inert solvent. (E) At a certain point, the micelles rupture and release a porous particle.
Scheme 1. (A,B) Suspension of monodisperse micron-sized polystyrene beads in water mixed with an emulsion consisting of GMA, EDMA, SDS, PVP, BPO, and 1-hexanol (in adequate quantities for S2, S3, and S4). For clarity, BPO (radical starter) is not included in the scheme. Hydrophobic attractions between PS and SDS are responsible for the formation of micelles. Water-soluble PVP stabilizes the micelles from the outside. (C) The particles swell due to the diffusion of GMA, EDMA, 1-hexanol, and BPO into the bead. (D) Upon polymerization, both methacrylates form the porous poly (glycidyl methacrylate-ethylene dimethacrylate) network with 1-hexanol as an inert solvent. (E) At a certain point, the micelles rupture and release a porous particle.
Polymers 13 01438 sch001
Publisher’s Note: MDPI stays neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Share and Cite

MDPI and ACS Style

Wagner, A.; Wagner, S.; Bredfeldt, J.-E.; Steinbach, J.C.; Mukherjee, A.; Kronenberger, S.; Braun, K.; Kandelbauer, A.; Mayer, H.A.; Brecht, M. Chemical Imaging of Single Anisotropic Polystyrene/Poly (Methacrylate) Microspheres with Complex Hierarchical Architecture. Polymers 2021, 13, 1438. https://doi.org/10.3390/polym13091438

AMA Style

Wagner A, Wagner S, Bredfeldt J-E, Steinbach JC, Mukherjee A, Kronenberger S, Braun K, Kandelbauer A, Mayer HA, Brecht M. Chemical Imaging of Single Anisotropic Polystyrene/Poly (Methacrylate) Microspheres with Complex Hierarchical Architecture. Polymers. 2021; 13(9):1438. https://doi.org/10.3390/polym13091438

Chicago/Turabian Style

Wagner, Alexandra, Stefanie Wagner, Jan-Erik Bredfeldt, Julia C. Steinbach, Ashutosh Mukherjee, Sandra Kronenberger, Kai Braun, Andreas Kandelbauer, Hermann A. Mayer, and Marc Brecht. 2021. "Chemical Imaging of Single Anisotropic Polystyrene/Poly (Methacrylate) Microspheres with Complex Hierarchical Architecture" Polymers 13, no. 9: 1438. https://doi.org/10.3390/polym13091438

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

Article Metrics

Back to TopTop