Lawrie Gwen, Keen Imelda, Drew Barry, Chandler-Temple Adrienne, Rintoul Llewellyn, Fredericks Peter, Grøndahl Lisbeth
School of Molecular and Microbial Sciences, The University of Queensland, Brisbane, Queensland 4072, Australia.
Biomacromolecules. 2007 Aug;8(8):2533-41. doi: 10.1021/bm070014y. Epub 2007 Jun 26.
This study investigates alginate-chitosan polyelectrolyte complexes (PECs) in the form of a film, a precipitate, as well as a layer-by-layer (LbL) assembly. The focus of this study is to fully characterize, using the complementary techniques of Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) in combination with solution stability evaluation, the interactions between alginate and chitosan in the PECs. In the FTIR spectra, no significant change in the band position of the two carbonyl vibrations from alginate occurs upon interaction with different ionic species. However, protonation of the carboxylate group causes a new band to appear at 1710 cm(-1), as anticipated. Partial protonation of the amine group of chitosan causes the appearance of one new band ( approximately 1530 cm(-1)) due to one of the -NH3+ vibrational modes (the other mode overlaps the amide I band). Importantly, the position of the two main bands in the spectral region of interest in partly protonated chitosan films is not dependent on the extent of protonation. XPS N 1s narrow scans can, however, be used to assess the degree of amine protonation. In our alginate-chitosan film, precipitate, and LbL assembly, the bands observed in the FTIR correspond to the species -COO- and -NH3+, but their position is not different from each of the single components. Thus, the conclusion of the study is that FTIR cannot be used directly to identify the presence of PECs. However, in combination with XPS (survey and narrow N 1s scans) and solution stability evaluation, a more complete description of the structure can be obtained. This conclusion challenges the assignment of FTIR spectra in the literature.
本研究调查了呈薄膜、沉淀物以及逐层(LbL)组装形式的海藻酸盐 - 壳聚糖聚电解质复合物(PEC)。本研究的重点是,结合溶液稳定性评估,使用傅里叶变换红外(FTIR)光谱和X射线光电子能谱(XPS)等互补技术,全面表征PEC中海藻酸盐与壳聚糖之间的相互作用。在FTIR光谱中,海藻酸盐的两个羰基振动带位置在与不同离子种类相互作用时没有显著变化。然而,正如预期的那样,羧酸盐基团的质子化导致在1710 cm⁻¹处出现一个新的谱带。壳聚糖胺基的部分质子化由于其中一种 -NH₃⁺振动模式(另一种模式与酰胺I带重叠)导致出现一个新的谱带(约1530 cm⁻¹)。重要的是,部分质子化的壳聚糖薄膜中感兴趣光谱区域的两个主要谱带位置不依赖于质子化程度。不过,XPS N 1s窄扫描可用于评估胺的质子化程度。在我们的海藻酸盐 - 壳聚糖薄膜、沉淀物和LbL组装体中,FTIR中观察到的谱带对应于 -COO⁻ 和 -NH₃⁺ 物种,但它们的位置与各单一成分的位置并无不同。因此,该研究的结论是FTIR不能直接用于识别PEC的存在。然而,结合XPS(全谱和N 1s窄扫描)以及溶液稳定性评估,可以获得更完整结构描述。这一结论对文献中FTIR光谱的归属提出了挑战。