Hydrophobic and Electrostatic Driving Forces for Ion Adsorption to Polymers and Extended Interfaces

离子吸附到聚合物和扩展界面的疏水和静电驱动力

• 批准号: 2004050
• 负责人: Paul Cremer
• 金额: $ 50万
• 依托单位: Pennsylvania State Univ University Park
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-09-01 至 2023-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2004050&HistoricalAwards=false
• 关键词: Hydrophobic; Electrostatic; Driving; Forces; Ion

The Macromolecular, Supramolecular, and Nanochemistry Program in the Chemistry Division supports Professor Paul S. Cremer and his students at the Pennsylvania State University to explore the ways that salts influence oily polymer molecules dissolved in water. Oil and water do not readily mix. In salad dressing, for example, an oily layer is typically found floating on top of a water-based layer. Moreover, dissolved salts reside primarily within the water phase rather than in the oil phase. Specifically, this study helps to determine when negatively or positively charged ions interact with polymer molecules or separate from them. The attraction of the polymer for salts in water dictates whether the polymers can remain dissolved in solution or deposit as a solid from the solution. The solubility of polymers in salt water is important in a surprisingly wide variety of areas ranging from the biological and food sciences to atmospheric chemistry, the self-assembly of novel materials, and even the cleaning of laundry. This research not sheds light on problems of direct relevance to society, but also trains students in interdisciplinary fields involving chemistry, biology, materials science, and engineering. Professor Cremer and his group are working with high school chemistry teachers to create inexpensive and easily accessible experiments for 10th and 11th graders. The instructors will develop teaching modules on principles of polymer solubility and the central role of salt ions in everyday life.The Cremer group is exploring how weakly hydrated anions, strongly hydrated cations, as well as hydronium and hydroxide influence the behavior of thermoresponsive polymers in aqueous solutions. Their experimental approach involves correlating ion binding and hydrophobic collapse behavior with spectroscopic signatures of the hydration shell. This information can be obtained by using techniques like Raman multivariate curve resolution spectroscopy and vibrational sum frequency spectroscopy. These thermodynamic and spectroscopic experiments are performed in collaboration with theoreticians performing molecular dynamic simulations. Measurements are made in bulk solution and with surfactant monolayers at the air/water interface. For example, results are being explored as a function of the size of the macromolecules as well as their net charges and the presence of specific negatively and positively charged functional groups. Special attention is focused on whether ions in solution can interact with polymer molecules via contact ion pairing or through solvent shared ion pairing. Moreover, the context in which charged moieties are presented is explored. These studies provide information as to how the number density of charged moieties as well as the configuration of surrounding hydrophobic sites influence ion-polymer interactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

化学系的大分子、超分子和纳米化学项目支持保罗·S·克雷默和他的学生在宾夕法尼亚州立大学探索盐影响溶解在水中的油性聚合物分子的方式。油和水不容易混合。例如，在沙拉酱中，通常发现油性层漂浮在水基层的顶部。此外，溶解的盐主要存在于水相中而不是油相中。具体来说，这项研究有助于确定带负电荷或正电荷的离子何时与聚合物分子相互作用或与它们分离。聚合物对水中盐的吸引力决定了聚合物是否可以保持溶解在溶液中或从溶液中以固体形式存款。聚合物在盐水中的溶解度在从生物和食品科学到大气化学、新材料的自组装甚至洗衣清洁的各种领域中非常重要。这项研究不仅揭示了与社会直接相关的问题，而且还培养了涉及化学，生物学，材料科学和工程的跨学科领域的学生。Cremer教授和他的团队正在与高中化学教师合作，为10年级和11年级的学生创造廉价且易于使用的实验。 教师将开发有关聚合物溶解性原理和盐离子在日常生活中的核心作用的教学模块。Cremer团队正在探索弱水合阴离子、强水合阳离子以及水合氢离子和氢氧化物如何影响温敏聚合物在水溶液中的行为。他们的实验方法涉及将离子结合和疏水性塌陷行为与水合壳的光谱特征相关联。这种信息可以通过使用像拉曼多元曲线分辨光谱和振动和频光谱的技术来获得。这些热力学和光谱实验是与进行分子动力学模拟的理论家合作进行的。在本体溶液中进行测量，并在空气/水界面处与表面活性剂单层。例如，正在探索结果作为大分子的大小以及它们的净电荷和特定的带负电荷和正电荷的官能团的存在的函数。特别注意的是，溶液中的离子是否可以通过接触离子配对或通过溶剂共享离子配对与聚合物分子相互作用。此外，在其中提出的带电部分的上下文进行了探讨。这些研究提供了关于带电部分的数量密度以及周围疏水位点的配置如何影响离子-聚合物相互作用的信息。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Local Electric Fields in Aqueous Electrolytes

• DOI: 10.1021/acs.jpcb.1c03257
• 发表时间: 2021-07-27
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY B
• 影响因子: 3.3
• 作者: Drexler, Chad, I;Cracchiolo, Olivia M.;Cremer, Paul S.
• 通讯作者: Cremer, Paul S.

Solvation Behavior of Elastin-like Polypeptides in Divalent Metal Salt Solutions

• DOI: 10.1021/acs.jpclett.3c02476
• 发表时间: 2023-11-03
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY LETTERS
• 影响因子: 5.7
• 作者: Zhao，Yani;Bharadwaj，Swaminath;van der Vegt，Nico F. A.
• 通讯作者: van der Vegt，Nico F. A.

Cation Identity Affects Nonadditivity in Salt Mixtures Containing Iodide and Sulfate

• DOI: 10.1007/s10953-021-01125-z
• 发表时间: 2021-11-12
• 期刊: JOURNAL OF SOLUTION CHEMISTRY
• 影响因子: 1.2
• 作者: Bui, Pho T.;Cremer, Paul S.
• 通讯作者: Cremer, Paul S.

Investigating oil solubilization into nonionic micelles by Raman multivariate curve resolution: Special Collection: Aggregation‐Induced Processes and Functions

通过拉曼多元曲线分辨率研究油溶解到非离子胶束中：特别收藏：聚集 - 诱导过程和功能

• DOI: 10.1002/agt2.385
• 发表时间: 2023
• 期刊: Aggregate
• 影响因子: 18.8
• 作者: Wentworth, Ciera M.;Myers, Ryan L.;Cremer, Paul S.;Zarzar, Lauren D.
• 通讯作者: Zarzar, Lauren D.

Contact Ion Pair Formation Is Not Necessarily Stronger than Solvent Shared Ion Pairing

• DOI: 10.1021/acs.jpclett.1c03576
• 发表时间: 2022-01-20
• 期刊: JOURNAL OF PHYSICAL CHEMISTRY LETTERS
• 影响因子: 5.7
• 作者: Judd, Kenneth D.;Gonzalez, Nicole M.;Cremer, Paul S.
• 通讯作者: Cremer, Paul S.