Distinguishing channel-type crystal structure from dispersed structure in β-cyclodextrin based polyrotaxanes via FTIR spectroscopy

doi:10.1007/s11706-011-0144-2

Front Mater Sci

2011, Vol. 5

Issue (3) : 329-334 https://doi.org/10.1007/s11706-011-0144-2

COMMUNICATION

Distinguishing channel-type crystal structure from dispersed structure in β-cyclodextrin based polyrotaxanes via FTIR spectroscopy

Jin WANG, Pei-Jing WANG, Peng GAO, Lan JIANG, Shuo LI, Zeng-Guo FENG(

)

School of Materials Science and Engineering, Beijing Institute of Technology, Beijing 100081, China

Download: PDF(296 KB) HTML
Export: BibTeX | EndNote | Reference Manager | ProCite | RefWorks

Abstract

Combining with XRD analysis, Fourier transform infrared (FTIR) spectroscopy is employed to discern the self-assembled structures of β-cyclodextrins (β-CDs) threaded onto the polymer backbone in the polyrotaxanes (PRs) by means of the relative changes of absorption intensity of the characteristic peaks of β-CDs at 1153 and 1025 cm^-1. For quantitative analysis, six parameters are proposed to describe the relative absorption intensity variations of these peaks associated with a channel-type crystal structure or a dispersed structure of β-CDs entrapped. Among them, absorbance ratio (AR), relative absorbance difference (RAD) and transmittance difference (TD) values are suitable. When the AR, RAD and TD data get below 1.04, 4.8 and 1.27, respectively, the PRs obtained would possess a dispersed structure. If these values go beyond 1.32, 34.5 and 9.47, respectively, they would hold a channel-type crystal structure. This finding provides a useful judgment to distinguish the self-assembled structures of β-CDs residing along the polymer backbone in the PRs.

Keywords FTIR polyrotaxane β-cyclodextrin self-assembled structure

Corresponding Author(s): FENG Zeng-Guo,Email:sainfeng@bit.edu.cn

Issue Date: 05 September 2011

Cite this article:

Jin WANG,Pei-Jing WANG,Peng GAO, et al. Distinguishing channel-type crystal structure from dispersed structure in β-cyclodextrin based polyrotaxanes via FTIR spectroscopy[J]. Front Mater Sci, 2011, 5(3): 329-334.

URL:

https://academic.hep.com.cn/foms/EN/10.1007/s11706-011-0144-2
https://academic.hep.com.cn/foms/EN/Y2011/V5/I3/329

Fig.1 Scheme 1 Chemical structure of β-CD and the as-prepared PRs.

Fig.2 XRD curves of the water and DMF treated PRs. Schematic description of the β-CD aggregated and dispersed structural PRs.

Fig.3 FTIR spectra of the water or DMF treated PRs.

Tab.1 The absorbance and transmittance data of the peaks at 1153 and 1025 cm and the calculated results for the parameters

Tab.2 Average value and standard deviation of six parameters for aggregated and dispersed structures

Fig.4 Criterion figures of the judgment of AR, RAD, and TD for dispersed and aggregated structures of PRs: green zone indicates aggregated structure and pink zone corresponds to dispersed structure.

1	Harada A, Kamachi M. Complex formation between poly(ethylene glycol) and α-cyclodextrins.Macromolecules, 1990, 23(10): 2821–2823 doi: 10.1021/ma00212a039
2	Wenz G, Han B H, Muller A. Cyclodextrin rotaxanes and polyrotaxanes.Chemical Reviews , 2006, 106(3): 782–817 doi: 10.1021/cr970027+
3	Harada A, Takashima Y, Yamaguchi H. Cyclodextrin-based supramolecular polymers.Chemical Society Reviews, 2009, 38(4): 875–882 doi: 10.1039/b705458k
4	Araki J, Ito K. Recent advances in the preparation of cyclodextrins-based polyrotaxanes and their application to soft materials.Soft Matter, 2007, 3(12): 1456–1473 doi: 10.1039/b705688e
5	Sarvothaman M K, Ritter H. Discriminating influence of α- and methylated β-cyclodextrins on complexation and polymerization of diacrylate and dimethacrylate monomers.Macromolecular Rapid Communications, 2004, 25(23): 1948–1952 doi: 10.1002/marc.200400348
6	Ito K. Novel cross-linking concept of polymer network: synthesis, structure, and properties of slide-ring gels with freely movable junctions.Polymer Journal, 2007, 39(6): 489–499 doi: 10.1295/polymj.PJ2006239
7	Michels J J, O’Connell M J, Taylor P N, et al. Synthesis of conjugated polyrotaxanes.Chemistry - A European Journal, 2003, 9(24): 6167–6176 doi: 10.1002/chem.200305245
8	Zhang X W, Zhu X Q, Tong X M, et al. Novel main-chain polyrotaxanes synthesized via ATRP of HPMA in aqueous media.Journal of Polymer Science, Part A: Polymer Chemistry, 2008, 46(15): 5283–5293 doi: 10.1002/pola.22856
9	Tong X M, Zhang X W, Ye L, et al. Novel main-chain polyrotaxanes synthesized via ATRP of HEMA initiated with polypseudorotaxanes comprising BriB-PEG-iBBr and α-CDs.Polymer, 2008, 49(21): 4489–4493 doi: 10.1016/j.polymer.2008.08.036
10	Zhang X W, Zhu X Q, Ke F Y, et al. Preparation and self-assembly of amphiphilic triblock copolymers with polyrotaxane as a middle block and their application as carrier for the controlled release of amphotericin B.Polymer, 2009, 50(18): 4343–4351 doi: 10.1016/j.polymer.2009.07.006
11	Tong X M. Zhang X W, Ye L, et al. Synthesis and characterization of block copolymers comprising a polyrotaxane middle block flanked by two brush-like PCL blocks.Soft Matter, 2009, 5(9): 1848–1855 doi: 10.1039/b818819j
12	Zhang X W, Ke F Y, Han J, et al. The self-aggregation behaviour of amphotericin B-loaded polyrotaxane-based triblock copolymers and their hemolytic evaluation.Soft Matter, 2009, 5(23): 4797–4803 doi: 10.1039/b914664d
13	Wang J, Gao P, Ye L, et al. Solvent- and thermoresponsive polyrotaxanes with β-cyclodextrin dispersed/aggregated structures on a Pluronic F127 backbone.The Journal of Physical Chemistry B, 2010, 114(16): 5342–5349 doi: 10.1021/jp101068b
14	Wang J, Gao P, Wang P J, et al. Novel polyrotaxanes comprising γ-cyclodextrins and Pluronic F127 end-capped with poly(N-isopropylacrylamide) showing solvent-responsive crystal structures.Polymer, 2011, 52(2): 347–355 doi: 10.1016/j.polymer.2010.12.014
15	Wang J, Ye L, Zhang A Y, et al. Novel triblock copolymers comprising a polyrotaxane middle block flanked by PNIPAAm blocks showing both thermo- and solvent-response.Journal of Materials Chemistry, 2011, 21(9): 3243–3250 doi: 10.1039/c0jm02803g
16	Wang J, Gao P, Ye L, et al. Dual thermo-responsive polyrotaxane-based triblock copolymers synthesized via ATRP of N-isopropylacrylamide initiated with self-assemblies of Br end-capped Pluronic F127 with β-cyclodextrins.Polymer Chemistry, 2011, 2(4): 931–940 doi: 10.1039/c0py00360c
17	Xie Z G, Hou D D, Ye L, et al. Enzyme-catalyzed preparation of supramolecular structured hydrogel of polypseudorotaxanes derived from the self-assembly of α-CDs with 3-arm p-hydroxyphenylpropionate terminated PEG.Frontiers of Materials Science in China , 2007, 1(4): 1–6
18	Hou D D, Geng X, Ye L, et al. Novel supramolecular hydrogels made via Michael-type addition reaction of dithiothreitol with self-assembly of α-cyclodextrins and acryloyl-terminated 3-arm PEG.Frontiers of Materials Science in China, 2010, 4(1): 70–77 doi: 10.1007/s11706-010-0010-7
19	Koening J L, Antoon M K. Thermally induced conformational changes in poly(vinyl chloride). Journal of Polymer Science, Polymer Physics Edition, 1977, 15(8): 1379–1395 doi: 10.1002/pol.1977.180150806
20	Painter P C, Havens J, Hart W W, et al. A Fourier transform infrared spectroscopic investigation of polyethylene single crystals. I. Methylene wagging mode.Journal of Polymer Science: Polymer Physics Edition, 1977, 15(7): 1223–1235 doi: 10.1002/pol.1977.180150708

[1]	Hui-Yun ZHOU, Ling-Juan JIANG, Yan-Ping ZHANG, Jun-Bo LI. β-Cyclodextrin inclusion complex: preparation, characterization, and its aspirin release in vitro[J]. Front Mater Sci, 2012, 6(3): 259-267.
[2]	B. ASWATHY, G. S. AVADHANI, S. SUJI, G. SONY. Synthesis of β-cyclodextrin functionalized gold nanoparticles for the selective detection of Pb²⁺ ions from aqueous solution[J]. Front Mater Sci, 2012, 6(2): 168-175.
[3]	LI Zai-feng, LI Jin-yan, SUN Jian, SUN Bao-qun, WANG Jin-jing, SHEN Qiang. Investigation of kinetics and morphology development for polyurethane-urea extended by DMTDA[J]. Front. Mater. Sci., 2008, 2(2): 200-204.

Viewed

Full text

Abstract

Cited

Shared

Discussed