Thien H Tran, Meghan Ricciardi, Lilly I Grunski, William C Wimley, Marcey L Waters, Bruce C Gibb
{"title":"Anion-Facilitated Hydrogen-Deuterium Exchange as a Tool to Probe Weak Anion-Protein Interactions Responsible for Hofmeister Effects.","authors":"Thien H Tran, Meghan Ricciardi, Lilly I Grunski, William C Wimley, Marcey L Waters, Bruce C Gibb","doi":"10.1021/acs.jpcb.4c08619","DOIUrl":"10.1021/acs.jpcb.4c08619","url":null,"abstract":"<p><p>Impeded by the complexity of proteinaceous structure and the very weak nature of the noncovalent interactions involved, the detailed mechanisms by which anions induce salting-in Hofmeister effects in proteins and peptides remain unclear. Here, using β-hairpin peptides as models, we examine two approaches to qualify (map) anion binding: <sup>1</sup>H NMR chemical shifts and hydronium-catalyzed hydrogen-deuterium exchange (HDX) rate changes. We demonstrate that each salt investigated─despite an affinity too weak to quantify accurately, caused denaturation to an extent that is both peptide and anion-specific, with more charge-diffuse anions inducing a greater degree of unfolding. Our studies reveal that the HDX mapping provides more detail than chemical shift data. Thus, HDX mapping reveals two slightly different mechanisms of denaturation, depending on the nature of the anion. Namely, assisted by a N-terminal Arg residue, charge-dense Cl<sup>-</sup> is chelated by the terminal N-H groups of the hairpin and induces a small degree of denaturation, whereas charge-diffuse anions intercalate deeply into the cation-π-hydrophobic core of the peptide and induce more substantial unfolding. These findings provide a glimpse of the different mechanisms by which anions can induce the salting-in Hofmeister effect in peptides and proteins and suggest HDX as a useful tool to map weak anion binding.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"2235-2245"},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11873968/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143404920","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Characteristics of Enthalpy Relaxation in Glassy d-Mannitol by Nanocalorimetry.","authors":"Zijian Wang, John H Perepezko","doi":"10.1021/acs.jpcb.4c06918","DOIUrl":"10.1021/acs.jpcb.4c06918","url":null,"abstract":"<p><p>d-Mannitol has attracted significant interest as a model system for understanding polyamorphism. In this study, the characteristics of enthalpy relaxation in d-mannitol glass are investigated using high-rate, high-precision nanocalorimetry under different controlled thermal histories. Key parameters, including glass-forming ability, liquid fragility, and activation energy for structural α relaxation, are determined by examining the dependence of crystallization enthalpy, limiting fictive temperature and glass transition temperature on cooling and heating rates. Isothermal physical aging experiments are conducted at temperatures significantly below the glass transition temperature over time scales spanning five decades. The kinetics of enthalpy relaxation is analyzed using the stretched exponential function, revealing that the extrapolated liquid line may not be reached by aging. A transition from slow β relaxation to α relaxation is identified through the Kissinger analysis across a range of heating rates. Further analysis of enthalpy relaxation using the absolute reaction rate theory reveals that the memory effect can occur without an increase in activation entropy during temperature up-jumps. These findings highlight d-mannitol as a compelling system for understanding relaxation behavior in glassy materials.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"2305-2317"},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439400","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Neel Shanmugam, Shubham Chatterjee, G Andrés Cisneros
{"title":"Impact of a Cancer-Associated Mutation on Poly(ADP-ribose) Polymerase1 Inhibition.","authors":"Neel Shanmugam, Shubham Chatterjee, G Andrés Cisneros","doi":"10.1021/acs.jpcb.4c07960","DOIUrl":"10.1021/acs.jpcb.4c07960","url":null,"abstract":"<p><p>Poly(ADP-ribose) polymerase1 (PARP1) plays a vital role in DNA repair, and its inhibition in cancer cells may cause cell apoptosis. In this study, we investigated the effects of a PARP1 variant, V762A, which is strongly associated with several cancers in humans, on the inhibition of PARP1 by three FDA-approved inhibitors: niraparib, rucaparib, and talazoparib. Specifically, we compared the inhibition of the mutant to that of wild-type (WT) PARP1. Additionally, we investigated how the mutation influences the binding of these inhibitors to PARP1. Our work suggests that while mutant PARP1 exhibits only minor differences in residual fluctuations, backbone deviations, and residue motion correlations compared to the WT under niraparib and rucaparib inhibitions, it shows significant and distinct differences in these features when inhibited by talazoparib. Among the three inhibitions, talazoparib inhibition uniquely lowers the average residue fluctuations in the mutant than the WT including lower fluctuations of mutant's N- and C-terminal residues in the catalytic domain, conserved H-Y-E traid residues, and donor loop (D-loop) residues which are important for catalysis more effectively than other inhibitions. However, talazoparib also significantly enhances destabilizing interactions between the mutation site in the HD domain in the mutant than WT. Further, among the three inhibitions, talazoparib inhibition uniquely and significantly disrupts the functional fluctuations of terminal regions in the mutant, which are otherwise present in the WT. The mutation and inhibition do not significantly affect PARP1's essential dynamics. Lastly, these inhibitors bind to the V762A mutant more effectively than to the WT, with similar binding free energies between them.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"2175-2186"},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143439403","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Protein Silencing with Self-Peptides.","authors":"Anoop Philip, Mayank Gupta, Shankha Banerjee, Arpan Dey, Debsankar Saha Roy, Aditya Shrivastava, Debasis Das, Sri Rama Koti Ainavarapu, Sudipta Maiti","doi":"10.1021/acs.jpcb.4c08265","DOIUrl":"10.1021/acs.jpcb.4c08265","url":null,"abstract":"<p><p>Designing functional molecules which can recognize and modify the activity of a specific protein is a frequently encountered challenge in biology and pharmaceutical chemistry, and requires major effort for each specific protein target. Here we demonstrate that \"self-peptides\", parts of folded proteins which by their nature are recognizable by the rest of the protein, provide a general route to developing such molecules. Such a synthetic peptide with a chemically prestabilized conformation can incorporate into the target protein during its folding, and can potentially displace its native counterpart to cause functional deficits. This strategy is especially promising for proteins with β-barrel topology, as the seam of the barrel provides a vulnerable target. We demonstrate this strategy by using green fluorescent protein (EGFP) as a model, as its fluorescence is a direct reporter of its conformation and function. Refolding EGFP in the presence of 35 μM of a disulfide-stabilized 20-residue self-peptide (SP1, which resembles a seam, strands 3 and 11, of GFP) quenches the fluorescence by 97%. A peptide with the same composition but a different sequence is only 40% as effective, demonstrating that silencing is relatively specific. Fluorescence correlation spectroscopy and time-resolved fluorescence lifetime measurements show that SP1 causes complete long-term fluorescence silencing of the EGFP molecules it incorporates into. This result can in principle have a biological application if the self-peptide incorporates into a protein during its synthesis, before the nascent protein folds. We show that SP1 can indeed silence nascent sfGFP (closely related to EGFP) during its ribosomal synthesis in an <i>in vitro</i> translation system. Therefore, self-peptides present a potentially general strategy for developing protein-specific silencers for physiological applications.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":"2215-2225"},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143412418","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Oskar Engberg, Debsankar Saha Roy, Pawel Krupa, Shankha Banerjee, Ankur Chaudhary, Albert A Smith, Mai Suan Li, Sudipta Maiti, Daniel Huster
{"title":"Molecules in the Serotonin-Melatonin Synthesis Pathway Have Distinct Interactions with Lipid Membranes.","authors":"Oskar Engberg, Debsankar Saha Roy, Pawel Krupa, Shankha Banerjee, Ankur Chaudhary, Albert A Smith, Mai Suan Li, Sudipta Maiti, Daniel Huster","doi":"10.1021/acs.jpcb.4c08750","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c08750","url":null,"abstract":"<p><p>The neurotransmitter serotonin is involved in physiological processes such as appetite, sleep, and mood and diseases such as anxiety and depression. Traditionally, the effects of serotonin were thought to be initiated by binding to its target transmembrane receptors. It is also known that serotonin can bind directly to the membrane with high affinity and modulate lipid dynamics, lateral segregation of lipids, vesicular association, and membrane protein activity. We investigated if other small molecules in the serotonin metabolic pathway, some of which are known to be signaling molecules while some others are not, have similar membrane modulating effects. Therefore, we examined serotonin and several of its metabolites: 5-hydroxytryptophan (5-HTP), serotonin, <i>N</i>-acetylserotonin (NAS), and melatonin in model membranes mimicking synaptic membranes. Using <sup>2</sup>H NMR spectroscopy of deuterated 1-palmitoyl-2-oleoyl-glycero-3-phosphocholine (POPC), we observed that all metabolites disorder the synaptic membrane-mimicking model membranes. The largest disordering effect was observed for NAS and the smallest for tryptophan. Using fluorescence correlation spectroscopy, it was found that only NAS promotes vesicular association similar to that of serotonin, while the others did not. Furthermore, we found that the serotonin metabolites differed in their membrane distribution by employing solid state <sup>1</sup>H magic angle spinning nuclear Overhauser enhancement spectroscopy (NOESY) experiments in simple POPC membranes. Similar results were obtained in synaptic membrane mimics using molecular dynamics simulations. In conclusion, while the causal correlation between membrane modulation effects and membrane distribution for the serotonin metabolites remains elusive, this study suggests that small-molecule metabolites and drugs can have drastic biological effects mediated through the membrane. The finding that small changes in structure lead to very different membrane modulation and distributions suggests the possibility of developing membrane modulating drugs in the future.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143522132","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Liangjie Wang, Fengjing Xu, Jinsong Gao, Jing Xu, Hao Zhu, Jinlong Li, Song Xie, Wei Liu, Yichang Liu
{"title":"Exploring the Adsorption Process of Iodinated Contrast Medias onto Phospholipid Membranes: A Theoretical Toxicity Evaluation Study.","authors":"Liangjie Wang, Fengjing Xu, Jinsong Gao, Jing Xu, Hao Zhu, Jinlong Li, Song Xie, Wei Liu, Yichang Liu","doi":"10.1021/acs.jpcb.4c07875","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c07875","url":null,"abstract":"<p><p>Iodinated contrast media (ICM) molecules are widely used in medical diagnostic imaging. With the increasing consumption of ICM, these compounds have been identified in groundwater and surface water systems. However, the effect of these environmental pollutants on living organisms remains inadequately studied. Herein, we employed molecular dynamics (MD) simulations to investigate the interactions between ICM molecules and the cell membranes. Our findings indicated that the entry behavior of ICM molecules into the membrane is dependent on their chemical structure. The insertion of ICM molecules affects the alignment of phospholipid headgroups and the order parameters of phospholipid tails, resulting in membrane thickness fluctuations. In addition, we observed that the distribution of ICM molecules in the membrane was related to the type of phospholipid. The proportions of phospholipids around the ICM molecules were different. Furthermore, the potential of mean force revealed that different ICM molecules had distinct free energy change characteristics when they transport from an aqueous environment to the membrane center. Some ICM molecules could access the membrane center after overcoming a small energy barrier, suggesting their potential transmembrane ability. This work systematically studied the effects of ICM on cell membranes, providing theoretical evidence for the environmental hazards of ICM.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143522130","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziwen Zhai, Jade Barreto, Daniel Hemmeter, Florian Maier, Hans-Peter Steinrück, Thomas M Koller
{"title":"Correlation of Macroscopic Surface Tension and Microscopic Surface Composition of Binary Ionic Liquid Mixtures with Common Cations and Anions of Different Size.","authors":"Ziwen Zhai, Jade Barreto, Daniel Hemmeter, Florian Maier, Hans-Peter Steinrück, Thomas M Koller","doi":"10.1021/acs.jpcb.4c08785","DOIUrl":"10.1021/acs.jpcb.4c08785","url":null,"abstract":"<p><p>We investigated the surface tension and surface composition of binary ionic liquid (IL) mixtures of ILs sharing the same cation. As model system, binary mixtures of 1-ethyl-3-methylimidazolium acetate ([C<sub>2</sub>C<sub>1</sub>Im][OAc], molar volume: 154.4 cm<sup>3</sup>·mol<sup>-1</sup> at 293 K) and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C<sub>2</sub>C<sub>1</sub>Im][Tf<sub>2</sub>N], molar volume: 256.2 cm<sup>3</sup>·mol<sup>-1</sup> at 293 K), with very different surface tensions, and with anions of very different chemical structure and size were studied over the whole composition range. The surface tension was obtained by pendant-drop (PD) measurements in the presence of 0.1 MPa argon between 294 and 323 K, and the surface composition was determined by angle-resolved photoelectron spectroscopy (ARXPS) in ultrahigh vacuum at 293 K. The ARXPS results reveal a strong preferential enrichment of [C<sub>2</sub>C<sub>1</sub>Im][Tf<sub>2</sub>N] at the vacuum-liquid interface of the binary mixtures, which is more pronounced at lower [C<sub>2</sub>C<sub>1</sub>Im][Tf<sub>2</sub>N] bulk contents. This microscopic behavior is reflected in the macroscopic surface tensions, which are significantly lower than calculated assuming a linear mixing behavior based on the bulk composition. A previously developed prediction model to correlate the surface tension with the molar surface composition yields deviations of more than 5% from the measured values, which we attribute to the strongly different sizes of the anions. By accounting for the surface areas occupied by the ILs, we present an improved new model which describes the experimental data very well within 1.4%.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514143","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Water Droplet and Its Contact Line Characteristics on Hydrophobic and Hydrophilic Surfaces: A Molecular Dynamics Simulation Approach.","authors":"Zahra Shamsi, Masumeh Foroutan","doi":"10.1021/acs.jpcb.4c08403","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c08403","url":null,"abstract":"<p><p>In literature, for a water droplet on a solid surface, the set of points at the intersection of the three phases, solid_ liquid_ gas, is referred to as the triple phase contact line (TPCL). However, recent studies indicate that the intersections of these phases form a region, which we refer to as the triple phase contact vicinity (TPCV). In the present work, the dimensions of the TPCV, including its width and cross-sectional area, have been calculated for a water droplet on a wide range of hydrophilic and hydrophobic surfaces, using molecular dynamics simulations. Additionally, the behavior of molecules, including their presence frequency, velocity, and displacement, has been studied. The results indicate that, as the surface becomes more hydrophobic, the width of the TPCV increases and its cross-sectional area decreases. The presence frequency of molecules located at the TPCV in equilibrium shows that the molecules are arranged in a Gaussian distribution and exhibit oscillatory movements around their average positions. It has also been shown that in equilibrium TPCV of hydrophobic surfaces, there are more molecules moving toward the center of the droplet relative to hydrophilic surfaces. Conversely, in equilibrium TPCV of hydrophilic surfaces, there are more molecules that move toward wetting the substrate relative to hydrophobic surfaces. Furthermore, for hydrophobic surfaces, the velocity of molecules moving toward the center of the droplet is greater than the velocity of molecules moving toward wetting the substrate. On hydrophilic surfaces, these two velocities are almost identical. Water molecules on hydrophobic surfaces move faster in all directions; however, on hydrophilic surfaces, they move slower in one direction. The density profile of the droplet on the surface shows that for hydrophobic surfaces, the highest density is reported at the center of the droplet. In contrast, for hydrophilic surfaces, due to the formation of layers of water molecules parallel to the substrate, the highest density is reported in the closest layer to the surface. At the end, considering the importance of graphene and its wettability behavior, which has recently attracted significant attention, the investigations related to the TPCV on the graphene surface are also reported.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143497567","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Impacts of External Electric Fields on Structures and Alignments of Ring Molecules.","authors":"Jiang Wang, Zhiling Li, Wenli Zhang","doi":"10.1021/acs.jpcb.4c06923","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c06923","url":null,"abstract":"<p><p>Ring molecules, which lack free ends, exhibit unique chemical and physical properties, making them promising candidates for nanodevice applications. Unlike their linear counterparts with two free ends, the behavior of ring molecules in water under external electric fields (EF) is not well understood. In this research, we employ molecular dynamics (MD) simulations to explore the structural and alignment behavior of two ring molecules of different sizes─C<sub>30</sub>H<sub>60</sub> and C<sub>60</sub>H<sub>120</sub>─in water, under 300 K, 1 bar and various EF conditions, including direct current EF (DC EF), alternating current EF (AC EF), and circular polarized EF (CP EF) at different frequencies. Our findings reveal the following: (1) both large and small rings exhibit two free energy minima. For C<sub>60</sub>H<sub>120</sub>, these correspond to collapsed and stretched configurations, while for C<sub>30</sub>H<sub>60</sub>, they represent open and closed configurations. (2) The applied EF can regulate the depth of these free energy minima. For C<sub>60</sub>H<sub>120</sub>, no EF, AC EF, and high-frequency CP EF favor the collapsed state, while DC EF and low-frequency CP EF promote the stretched configuration. In the case of C<sub>30</sub>H<sub>60</sub>, no EF and high-frequency CP EF favor the open-ring state, whereas all other EF conditions tend to close the ring. (3) Both ring molecules align with the directional EF to minimize disruption of the hydrogen-bond network, with C<sub>60</sub>H<sub>120</sub> showing a stronger alignment effect than C<sub>30</sub>H<sub>60</sub> due to its longer structure. (4) Under CP EF, ring molecules exhibit rotation driven by the rotating EF, but there is a lag in the angle between the EF vector and the molecule's elongation. Higher frequency CP EF shows less ability to capture and align the molecule. This research enhances our understanding of how ring molecules behave in water under external EF and provides a theoretical foundation for future engineering applications involving controlled manipulation of these molecules.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":" ","pages":""},"PeriodicalIF":2.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143514153","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Caroline Fatina, Junguang Yu, Ranko Richert and Lian Yu*,
{"title":"Structural Evolution in a Glass-Forming Liquid Alcohol by X-Ray Scattering: Contrasting Behaviors of Main Peak and Prepeak Structures","authors":"Caroline Fatina, Junguang Yu, Ranko Richert and Lian Yu*, ","doi":"10.1021/acs.jpcb.4c0682210.1021/acs.jpcb.4c06822","DOIUrl":"https://doi.org/10.1021/acs.jpcb.4c06822https://doi.org/10.1021/acs.jpcb.4c06822","url":null,"abstract":"<p >X-ray scattering of liquid 2-ethyl-1-hexanol (2E1H) has been measured from its liquid state to its glassy state with focus on the main scattering peak and the prepeak. The main peak, associated with the packing of the alkyl chains, shifts to higher angle and sharpens in a manner consistent with closely packed spheres, until kinetic arrest at the glass transition temperature <i>T</i><sub>g</sub> (146 K). In contrast, the prepeak, associated with the correlation of the hydroxyl groups separated by the hydrocarbon chains, shows a transition near 220 K, below which its width is nearly frozen and insensitive to the passage of <i>T</i><sub>g</sub>. This transition coincides with a similar transition in the Kirkwood factor <i>g</i><sub>K</sub> which reports the orientational correlation of the OH dipoles, and with the transition reported previously as the “250 K anomaly” based on other observables. This transition arises from the increased hydrogen bonding between the hydroxyl groups and the resulting improvement of the regularity of the alcohol bilayers.</p>","PeriodicalId":60,"journal":{"name":"The Journal of Physical Chemistry B","volume":"129 9","pages":"2505–2513 2505–2513"},"PeriodicalIF":2.8,"publicationDate":"2025-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547692","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}