The hydration energy of an ion largely resides within the first few layers of water molecules in its hydration shell. Hence, it is important to understand the transformation of water properties, such as hydrogen-bonding, intermolecular vibrational coupling, and librational freedom in the hydration shell of ions. We investigated these properties in the hydration shell of mono- (Cl(-) and I(-)) and bivalent (SO4(2-) and CO3(2-)) anions by using Raman multivariate curve resolution (Raman-MCR) spectroscopy in the OH stretch, HOH bend, and [bend+librational] combination bands of water. Raman-MCR of aqueous Na-salt (NaCl, NaI, Na2SO4, and Na2CO3) solutions provides ion-correlated spectra (IC-spectrum) which predominantly bear the vibrational characteristics of water in the hydration shell of respective anions. Comparison of these IC-spectra with the Raman spectrum of bulk water in different spectral regions reveals that the water is vibrationally decoupled with its neighbors in the hydration shell. Hydrogen-bond strength and librational freedom also vary with the nature of anion: hydrogen-bond strength, for example, decreases as CO3(2-) > SO4(2-) > bulk water ≈ Cl(-) > I(-); and the librational freedom increases as CO3(2-) ≈ SO4(2-) < bulk water < Cl(-) < I(-). It is believed that these structural perturbations influence the dynamics of coherent energy transfer and librational reorientation of water in the hydration shell of anions.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1063/1.4899070 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Scaling Behavior and Conductance Mechanisms of Ion Transport in Atomically Thin Graphene Nano/Subnanopores.
Nano Lett
January 2025
The Key Laboratory of Weak Light Nonlinear Photonics, Ministry of Education, School of Physics and Teda Applied Physics Institute, Renewable Energy Conversion and Storage Center, State Key Laboratory of Photovoltaic Materials and Cells, Nankai University, Tianjin 300071, China.
Ion transport through atomically thin nano/subnanopores, such as those in monolayer graphene, presents challenges to traditional ion conduction models, primarily due to extreme confinement effects and hydration interactions. Under these conditions, existing models fail to account for conductance behaviors at the nano- and subnanometer scales. In this study, we perform a combined experimental and theoretical investigation of ion transport in monolayer graphene nano/subnanopores across varying salt concentrations.
View Article and Find Full Text PDFAffinity for OH Produces Four-Coordinated Zn Impurities in Hydrated Amorphous Calcium Carbonate.
Inorg Chem
January 2025
Physical and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States.
Using ab initio based molecular dynamics and electronic structure calculations, we show that Zn impurities in hydrated amorphous calcium carbonate (ACC) have a much lower coordination number than other divalent impurities due to covalent interactions between the 3d Zn shell and the oxygen atoms of the carbonate and water groups. The local structure around Zn in ACC, including the predicted low coordination number, is confirmed by X-ray absorption spectroscopy of synthetic Zn-bearing ACC. The strong Zn-O chemical interaction leads to substantial water dissociation and slightly disrupts the hydrogen bonding network.
View Article and Find Full Text PDFInhibiting Friction-Induced Exogenous Adhesion via Robust Lubricative Core-Shell Nanofibers for High-Quality Tendon Repair.
Biomacromolecules
January 2025
Department of Hepatobiliary Surgery, Hebei International Joint Research Center for Digital Twin Diagnosis and Treatment of Digestive Tract Tumors, Baoding Key Laboratory of Precision Diagnosis and Treatment of Digestive Tract Tumors, Affiliated Hospital of Hebei University, Baoding 071000, China.
Friction is the trigger cause for excessive exogenous adhesion, leading to the poor self-repair of the tendon. To address this problem, we developed electrospun dual-functional nanofibers with surface robust superlubricated performance and bioactive agent delivery to regulate healing balance by reducing exogenous adhesion and promoting endogenous healing. Coaxial electrospinning and our previous developed in situ robust nanocoating growth techniques were employed to create the lubricative/repairable core-shell structured nanofibrous membrane (L/R-NM).
View Article and Find Full Text PDFAdsorption of Eu and Gd on high-charge micas as inner-sphere complexes.
J Colloid Interface Sci
January 2025
Departamento QUIPRE, Universidad de Cantabria, Avda. Los Castros 46 39005 Santander, Spain; Grupo de Nanomedicina, IDIVAL, Avda. Cardenal Herrera Oria s/n, 39011 Santander, Spain. Electronic address:
High-charge micas exhibit improved adsorption properties and are a promising alternative clay material for the engineered barrier in deep geological repositories. When combined with Eu cations, they serve as an in situ luminescent probe for tracking the physical-chemical changes occurring in this engineered barrier over the long term. Therefore, a better understanding of the local environment of the lanthanide is highly desirable to comprehend the specific behavior of these systems.
View Article and Find Full Text PDFFAP-targeting biomimetic nanosystem to restore the activated cancer-associated fibroblasts to quiescent state for breast cancer radiotherapy.
Int J Pharm
January 2025
Department of Pharmacy, Union Hospital, Tongji Medical College, Huazhong University of Science and Technology, Wuhan, 430022, China; Hubei Province Clinical Research Center for Precision Medicine for Critical Illness, Wuhan, 430022, China. Electronic address:
Cancer associated fibroblasts (CAFs) are one of the most important stromal cells in the tumor microenvironment, playing a pivotal role in the development, recurrence, metastasis, and immunosuppression of cancer and treatment resistance. Here, we developed a core-shell biomimetic nanosystem termed as FAP-C NPs. This system was comprised of 4T1 extracellular vesicles fused with a FAP single-chain antibody fragment to form the biomimetic shell, and PLGA nanoparticles loaded with calcipotriol as the core.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!