Microsolvation and hydration enthalpies of CaS2O3(H2O) n (n = 0–19) and S2O3 2−(H2O) n (n = 0–16): an ab initio study

Rosas-García, Víctor M.; Sáenz-Tavera, Isabel del Carmen; Rodríguez-Herrera, Verónica Janeth; Garza-Campos, Benjamín Raymundo

doi:10.1007/s00894-015-2638-9

Cited by 9 publications

(1 citation statement)

References 31 publications

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“…These simulations revealed that 8.9 water molecules were required to complete the first solvation shell of thiosulfate, and 3.5 water molecules were present around the terminal S atom. The ab initio study of S 2 O 3 2– (H 2 O) n ( n = 0–16) clusters highlighted the presence of 15 water molecules in the first solvation shell of thiosulfate. However, the ultrasonic velocity data of an aqueous solution of thiosulfate predicted the appearance of 13 water molecules in the first solvation shell of the thiosulfate ion .…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules

Biswas

Mallik

2019

J. Phys. Chem. B

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We performed first-principles molecular dynamics simulations of relatively dilute aqueous solutions of sulfate and thiosulfate dianions to analyze the structure, dynamics, and vibrational spectral properties of water molecules around the solute, especially the spatially patterned solvent molecules in the first solvation layer and the extended layers. This study also involves the investigation of dynamics of dangling OH groups in these layers and their role in patterning the water molecules around the dianions. Structural evaluation of the systems is carried out by radial distribution functions, number integrals, and spatial distribution functions. The lifetime of dangling OH groups inside the solvation shell is compared more to that of the bulk. By constructing the O−H groups in three ensembles (S1, S2, and S3) around the anion, we show that the frequency distribution of OH modes in the S1 ensemble show red-shifting for both sulfate and thiosulfate. The O−H groups in the S2 ensemble of the sulfate−water system show red-shifting by 10 cm −1 , while in the case of thiosulfate−water, these O−H groups show blue-shifting by 8 cm −1 . The water molecules in S1 and S2 subensembles have slower dynamics compared to those in the bulk (S3). The dynamics of various kinds of hydrogen bonds were characterized by hydrogen bond population correlation functions. The spectral diffusion of solvation shell O−H modes was performed through a frequency−time correlation function. We find a significant amount of orientational retardation of water molecules in the S1 layer and moderate retardation in the S2 layer as compared to that in the bulk, S3 layer. All these findings, the red shift of the OH stretching frequency in S1 and S2 layers, slowing down of the orientational dynamics of OH vectors in S1 and S2 layers, and less diffusivity of water in S1 and S2 layers, show the long-range kosmotropic effect of multivalent sulfate and thiosulfate oxyanions. Due to the long-range effect, heterogeneous occupancy of water molecules is observed, and the water molecules are found to arrange in a patterned manner in the vicinity of anions with varied local density.

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Section: Introductionmentioning

confidence: 99%

Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules

Biswas

Mallik

2019

J. Phys. Chem. B

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Cell-Derived Microparticles/Exosomes in Neuroinflammation

Horstman

Ahn

2017

Inflammatory Disorders of the Nervous System

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Inhibition of p16INK4A to Rejuvenate Aging Human Cardiac Progenitor Cells via the Upregulation of Anti-oxidant and NFκB Signal Pathways

Khatiwala

Zhang

et al. 2018

Stem Cell Rev and Rep

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Autologous human cardiac stem/progenitor cell (hCPC) therapy is a promising treatment that has come into use in recent years for patients with cardiomyopathy. Though innovative in theory, a major hindrance to the practical application of this treatment is that the hCPCs of elderly patients, who are most susceptible to myocardial disease, are senescent and prone to cell death. Rejuvenating hCPCs from elderly patients may help overcome this obstacle, and can be accomplished by reversing entry into the cellular stage of senescence. p16, a cyclin dependent kinase inhibitor, is an important player in the regulation of cell senescence. In this study, we investigated whether knockdown of p16 will rejuvenate aging hCPCs to a youthful phenotype. Our data indicated that upregulation of p16 is associated with hCPC senescence. Both cell proliferation and survival capacity were significantly increased in hCPCs infected with lentivirus expressing p16 shRNA when compared to control hCPCs. The knockdown of p16 also induced antioxidant properties as indicated by a 50% decrease in ROS generation at basal cell metabolism, and a 25% decrease in ROS generation after exposure to oxidative stress. Genes associated with cell senescence (p21), anti-apoptosis (BCL2 and MCL1), anti-oxidant (CYGB, PRDX1 and SRXN1), and NFκB signal pathway (p65, IKBKB, HMOX1, etc.), were significantly upregulated after the p16 knockdown. Knocking down the NFĸB-p65 expression also significantly diminished the cytoprotective effect caused by the p16 knockdown. Our results suggest that genetic knockdown of p16 may play a significant role in inducing antioxidant effects and extending lifespan of aging hCPCs. This genetic modification may enhance the effectiveness of autologous hCPC therapy for repair of infarcted myocardium.

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Microsolvation and hydration enthalpies of CaS2O3(H2O) n (n = 0–19) and S2O3 2−(H2O) n (n = 0–16): an ab initio study

Cited by 9 publications

References 31 publications

Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules

Heterogeneous Occupancy and Vibrational Dynamics of Spatially Patterned Water Molecules

Cell-Derived Microparticles/Exosomes in Neuroinflammation

Inhibition of p16INK4A to Rejuvenate Aging Human Cardiac Progenitor Cells via the Upregulation of Anti-oxidant and NFκB Signal Pathways

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