Terahertz fingerprint reveals the effect of alcohols on sodium ions hydration shell.

Ion hydration plays a crucial role in numerous fundamental processes. Various spectroscopic methods are employed to investigate the slowing down of hydration bond dynamics in the proximity of both anions and cations. To date, most of these studies have primarily focused on the properties of binary systems. However, in comparison to ion-water binary systems, ternary systems that involve ions, water, and organic matter are more prevalent in nature and provide more realistic insights into biological processes. This study focuses on ion hydration in water and alcohol mixture using terahertz spectroscopy and x-ray diffraction (XRD). The results reveal a distinct behavior depending on the type of alcohol used. Specifically, the presence of both methanol and ethanol results in the disappearance of absorption peaks associated with NaCl hydrate at low temperatures. In contrast, tert-butanol does not exhibit such an effect, and isopropanol demonstrates a more complex response. By combining these terahertz spectroscopic findings with low-temperature XRD data, we gain insights into the formation, or lack thereof, of NaCl · 2H2O hydrate crystals. Crucially, our observations suggest a dominant correlation between the polarity of the alcohol molecules and its impact on the Na+ hydration. Strongly polar alcohols preferentially solvating the Na+ ion lead to the failure of hydrate formation, while weakly polar alcohols do not have this effect.

Water hydration of polyethylene glycol dimethyl ether.

In this work, GHz and THz complex dielectric spectra of a polyethylene glycol dimethyl ether (2000 g/mol) aqueous solution were studied. The reorientation relaxation of water in this kind of macro-amphiphilic molecule solution can be well described by three Debye models, including under-coordinated water, bulk-like water [water molecules in a tetrahedral hydrogen bond network (bulk water) and bulk water molecules affected by hydrophobic groups], and slow hydrating water (water molecules donating hydrogen bonds to hydrophilic ether groups). The reorientation relaxation timescales of bulk-like water and slow hydration water both show increases with concentration from 9.8 to 26.7 ps and from 46.9 to 100.1 ps, respectively. By estimating the ratios of the dipole moment of slow hydration water to the dipole moment of bulk-like water, we calculated the experimental Kirkwood factors of bulk-like and slow hydrating water. The experimental Kirkwood factor of bulk-like water increased from 3.17 to 3.44 with concentrations, while the experimental Kirkwood factor of slow hydrating water roughly remained constant at 4.13 from concentrations of 15%-60%. The estimated water molecule numbers of three water components around monomers also confirm our sorting for water components.

Monitoring MgCl2 hydrate formation from aqueous solutions using terahertz time-domain spectroscopy.

The interaction of MgCl2 with H2O is heavily involved in biological and chemical processes. In this work, freezing-induced hydrate formation from MgCl2 aqueous solution was monitored using terahertz time-domain spectroscopy. At low temperatures, two phase transitions from brine to hydrate formation could be clearly observed, and the formation of hydrate was accompanied by the emergence of new THz fingerprint peaks at 1.02, 1.56, and 1.84 THz, respectively. Integrating XRD and quantum chemical calculations, we attributed the absorption peaks to the vibrational modes of the formed MgCl2·12H2O. This demonstrates the potential of THz spectroscopy for application in the detection of biological processes in low-temperature environments, such as cell freezing.

Water dynamics in the hydration shell of hyper-branched poly-ethylenimine.

We performed THz and GHz dielectric relaxation spectroscopy to investigate the reorientational dynamics of water molecules in the hydration shell of amphiphilic hyper-branched poly-ethylenimine (HPEI). Four Debye equations were employed to describe four types of water in the hydration shell, including bulk-like water, under-coordinated water, slow water (water molecules hydrating the hydrophobic groups and water molecules accepting hydrogen bonds from the NH2 groups) and super slow water (water molecules donating hydrogen bonds to and accepting hydrogen bonds from NH groups). The time scales of undercoordinated and bulk-like water show a slight decline from 0.4 to 0.1 ps and from 8 to 2 ps, respectively. Because of hydrophilic amino groups, HPEI molecules exhibit a strong retardation effect, where the time scales of slow and super slow water increase with concentration from 17 to 39.9 ps and from 88 to 225 ps, respectively.

The supramolecular synthon behavior within cocrystals of pyrazinamide and alkyl dicarboxylic acids: A perspective from terahertz spectroscopy and quantum chemical calculation.

Pyrazinamide (PZA) is a widely-used anti-tuberculosis pharmaceutical, but its poor solubility prompts us to optimize pharmaceutical performance. Cocrystallization is a promising technique to improve physiochemical properties of active pharmaceutical ingredient (API) by connecting it with cocrystal former (CCF) via intermolecular interactions. Even though a series of alkyl dicarboxylic acids are employed to form cocrystal structures, systematic understanding on the role of intermolecular interactions is still missing. Therefore, terahertz (THz) spectroscopy and quantum chemical calculation are combined to elucidate the behavior of ubiquitous supramolecular synthons, such as hetero-synthons of acid-pyrazine, acid-amide and homo-synthon of amide-amide, from energy's view. Potential energy is calculated to differentiate the stability within polymorphs of PZA-MA cocrystal and free energy is evaluated to compare the solubility of PZA-CCF cocrystals respectively. With regard to vibrational energy, THz spectral fingerprints are theoretically assigned to specific vibrations and attributed to the flexibility deformation of supramolecular synthons based on oscillation theory, where stretching and twisting modes dominate the collective vibrational behavior. It provides a promising tool to evaluate cocrystal performance from its driving force and insightful guidance to discover new pharmaceutical cocrystals.

The collective vibrational modes of dihydropyridine in nifedipine studied by terahertz spectroscopy.

Cardiovascular pharmaceuticals have drawn huge attention in drug development. Nifedipine (NFD) is an important member of calcium channel blockers (CCB) with the structural characteristic of dihydropyridine (DHP), but the binding mechanism to its target remains an open question. Even though several analytical techniques have been used for structural characterizations, the information of collective vibrational behavior is still lacking. In this work, we use terahertz (THz) spectroscopy to investigate the spectral fingerprints of NFD, and quantitatively evaluate the temperature-induced frequency shifts. Combined with quantum chemical calculations, each THz fingerprint is attributed to specific collective vibrational modes. The collective vibrations of DHP are mainly distributed below 2.5 THz, which provides complementary information to understand the behavior of rigid DHP ring. The rotation of methyl group and the wagging of nitrophenyl group are widely distributed in the range of 1.0-4.0 THz, which is helpful for the conformational recognition between NFD and target molecule. THz spectroscopy is demonstrated to be suitable for characterizing the collective vibrational modes of DHP and elucidating the drug-target binding behavior from the perspective of noncovalent interactions. It has the potential to become a non-invasive technology for conformational analysis and pharmaceutical development.

Exploring the Application of Multi-Resonant Bands Terahertz Metamaterials in the Field of Carbohydrate Films Sensing.

Terahertz spectroscopy is a powerful tool for investigating the properties and states of biological matter. Here, a systematic investigation of the interaction of THz wave with "bright mode" resonators and "dark mode" resonators has been conducted, and a simple general principle of obtaining multiple resonant bands has been developed. By manipulating the number and positions of bright mode and dark mode resonant elements in metamaterials, we realized multi-resonant bands terahertz metamaterial structures with three electromagnetic-induced transparency in four-frequency bands. Different carbohydrates in the state of dried films were selected for detection, and the results showed that the multi-resonant bands metamaterial have high response sensitivity at the resonance frequency similar to the characteristic frequency of the biomolecule. Furthermore, by increasing the biomolecule mass in a specific frequency band, the frequency shift in glucose was found to be larger than that of maltose. The frequency shift in glucose in the fourth frequency band is larger than that of the second band, whereas maltose exhibits an opposing trend, thus enabling recognition of maltose and glucose. Our findings provide new insights into the design of functional multi-resonant bands metamaterials, as well as new strategies for developing multi-band metamaterial biosensing devices.

Stability and Stabilization of Nash Equilibrium for Uncertain Noncooperative Dynamical Systems With Zero-Sum Tax/Subsidy Approach.

A zero-sum tax/subsidy approach for stabilizing unstable Nash equilibria in pseudo-gradient-based noncooperative dynamical systems is proposed without the information of agents' personal sensitivity parameters. Specifically, we first present several sufficient conditions for guaranteeing stability of an unstable Nash equilibrium in the face of uncertainty. Furthermore, we develop a framework where a system manager constructs a zero-sum tax/subsidy incentive structure by collecting taxes from some agents and giving the same amount of subsidy in total to other agents so that the agents' payoff structure is properly modified. Finally, we present several numerical examples to illustrate the utility of the zero-sum tax/subsidy approach.