Pereira A A, Martins G F, Antunes P A, Conrrado R, Pasquini D, Job A E, Curvelo A A S, Ferreira M, Riul A, Constantino C J L
DFQB, Faculdade de Ciências e Tecnologia, UNESP, Presidente Prudente, SP, Brazil.
Langmuir. 2007 Jun 5;23(12):6652-9. doi: 10.1021/la063582s. Epub 2007 May 10.
Four lignin samples were extracted from sugar cane bagasse using four different alcohols (methanol, ethanol, n-propanol, and 1-butanol) via the organosolv-CO2 supercritical pulping process. Langmuir films were characterized by surface pressure vs mean molecular area (Pi-A) isotherms to exploit information at the molecular level carrying out stability tests, cycles of compression/expansion (hysteresis), subphase temperature variations, and metallic ions dissolved into the water subphase at different concentrations. Briefly, it was observed that these lignins are relatively stable on the water surface when compared to those obtained via different extraction processes. Besides, the Pi-A isotherms are shifted to smaller molecular areas at higher subphase temperatures and to larger molecular areas when the metallic ions are dissolved into the subphase. The results are related to the formation of stable aggregates (domains) onto the water subphase by these lignins, as shown in the Pi-A isotherms. It was found as well that the most stable lignin monolayer onto the water subphase is that extracted with 1-butanol. Homogeneous Langmuir-Blodgett (LB) films of this lignin could be produced as confirmed by UV-vis absorption spectroscopy and the cumulative transfer parameter. In addition, FTIR analysis showed that this lignin LB film is structured in a way that the phenyl groups are organized preferentially parallel to the substrate surface. Further, these LB films were deposited onto gold interdigitated electrodes and ITO and applied in studies involving the detection of Cd+2 ions in aqueous solutions at low concentration levels through impedance spectroscopy and electrochemical measurements. FTIR spectroscopy was carried out before and after soaking the thin films into Cd+2 aqueous solutions, revealing a possible physical interaction between the lignin phenyl groups and the heavy metal ions. The importance of using nanostructured systems is demonstrated as well by comparing both LB and cast films.
通过有机溶剂-二氧化碳超临界制浆工艺,使用四种不同的醇(甲醇、乙醇、正丙醇和正丁醇)从甘蔗渣中提取了四种木质素样品。通过表面压力与平均分子面积(π-A)等温线对朗缪尔膜进行表征,以在分子水平上获取信息,进行稳定性测试、压缩/膨胀循环(滞后)、亚相温度变化以及不同浓度下溶解于水亚相中的金属离子研究。简而言之,与通过不同提取工艺获得的木质素相比,观察到这些木质素在水面上相对稳定。此外,π-A等温线在较高亚相温度下向较小分子面积移动,而当金属离子溶解于亚相时向较大分子面积移动。结果与这些木质素在水亚相上形成稳定聚集体(区域)有关,如π-A等温线所示。还发现,在水亚相上最稳定的木质素单分子层是用正丁醇提取的。紫外可见吸收光谱和累积转移参数证实,可以制备这种木质素的均匀朗缪尔-布洛杰特(LB)膜。此外,傅里叶变换红外光谱分析表明,这种木质素LB膜的结构使得苯基优先平行于基底表面排列。此外,将这些LB膜沉积在金叉指电极和氧化铟锡上,并应用于通过阻抗谱和电化学测量检测低浓度水溶液中Cd²⁺离子的研究。在将薄膜浸泡在Cd²⁺水溶液之前和之后进行了傅里叶变换红外光谱分析,揭示了木质素苯基与重金属离子之间可能存在的物理相互作用。通过比较LB膜和流延膜,也证明了使用纳米结构系统的重要性。