The Journal of Physical Chemistry B最新文献

To enhance crude oil recovery under complex reservoir conditions and reduce the environmental impact of the oil displacement system, a biosurfactant lipid peptide (TH) was combined with four chemical surfactants. From these combinations, those capable of achieving an ultralow interfacial tension region (<10^-2 mN/m) were selected. The selected surfactant mixtures were then combined with polyacrylamide (HPAM) to construct a surfactant-polymer binary oil displacement system. The results showed that TH/OAB(2:1), TH/OAB(3:1), and TH/EAO(3:1) could reduce IFT to the ultralow interfacial tension region. Compound surfactants are easier to form mixed micelles than single surfactants, and the EACN of TH/OAB(2:1) and TH/EAO(3:1) is consistent with EACN_Oil, which can achieve higher surface activity at lower concentrations. The three compound surfactants have a wide range of ultralow interfacial tension concentrations and excellent antidilution performance. TH/OAB(2:1) and TH/EAO(3:1) have better antiformation adsorption performance than TH/OAB(3:1), and the oil washing rate of TH/OAB(2:1) is up to 80.30%. TH and OAB have spatial complementarity, which can increase the molecular packing density at the oil-water interface and reduce the IFT. In CaCl₂ and NaCl solutions, the IFT of the two binary flooding systems constructed by TH/OAB(2:1) and TH/EAO(3:1) and HPAM remained in the ultralow interfacial tension region, with excellent salt resistance. When aged in the reservoir for 90 days, the IFT slightly increased but the viscosity decreased significantly. Adding a viscosity retaining agent (JW) was required to maintain the viscosity of the system. In the simulated oil displacement experiment, the recovery improvement of the two binary oil displacement systems was higher than those of surfactant and polymer alone. This study provides a new idea for the alkali-free surfactant-polymer binary oil flooding system and provides theoretical support for the practical application of TH in tertiary oil recovery.

Protein aggregation resulting in either ordered amyloids or amorphous aggregates is not only restricted to deadly human diseases but also associated with biotechnological challenges encountered in the therapeutic and food industries. Elucidating the key structural determinants of protein aggregation is important to devise targeted inhibitory strategies, but it still remains a formidable task owing to the underlying hierarchy, stochasticity, and complexity associated with the self-assembly processes. Additionally, alterations in solution pH, salt types, and ionic strength modulate various noncovalent interactions, thus affecting the protein aggregation propensity and the aggregation kinetics. However, the molecular origin and a detailed understanding of the effects of weakly and strongly hydrated salts on protein aggregation and their plausible roles in the dissolution of aggregates remain elusive. In this study, using fluorescence and circular dichroism spectroscopy in combination with electron microscopy and light scattering techniques, we show that the ionic size, valency, and extent of hydration of cations play a crucial role in regulating the protein aggregation and disaggregation processes, which may elicit unique methods for governing the balance between protein self-assembly and disassembly.

Advances in Alzheimer's disease (AD) are related to the oligomerization of Amyloid β (Aβ) peptides. Therefore, alteration of the process can prevent AD. We investigated the Aβ₄₂ dimerization under the effects of gold nanoparticles using temperature replica-exchange molecular dynamics (REMD) simulations. The structural change of dimers in the presence and absence of the gold nanoparticle, Au₅₅, was monitored over stable intervals. Physical insights into the oligomerization of Aβ were thus clarified. The computed metrics indicate that Au₅₅ affects the progress of oligomerization. Specifically, the presence of the gold nanoparticle significantly modifies the structure of dimeric Aβ₄₂. The β-content experienced a substantial decrease with the induction of Au₅₅. The turn and coil-contents are also decreased under the effects of the gold nanoparticle. However, the α-content of the dimer exhibited a rigid increase. The influence of gold nanoparticles on the dimeric Aβ₄₂ differs significantly from that of silver nanoparticles, which reduce β-content but increase coil-, turn-, and α-contents. The nature of inhibition will be discussed, in which the vdW interaction plays a driving force for the interaction between the Aβ₄₂ dimer and the gold nanoparticle.

Interactions of the peptide substance P (SP) (RPKPQQFFGLM-NH₂) with trimethylamine N-oxide (TMAO) were investigated by using cryo-ion mobility-mass spectrometry (cryo-IM-MS), variable-temperature (278-358 K) electrospray ionization (vT-ESI) MS, and molecular dynamics (MD) simulations. Cryo-IM-MS provides evidence that cold solutions containing SP and TMAO yield abundant hydrated SP dimer ions, but dimer formation is inhibited in solutions that also contain urea. In addition, we show that SP dimer formation at cold solution temperatures (<298 K) is favored when TMAO interacts with the hydrophobic C-terminus of SP and is subject to reduced entropic penalty when compared to warmer solution conditions (>298 K). MD simulations show that TMAO lowers the free energy barrier for dimerization and that monomers dimerize by forming hydrogen bonds (HBs). Moreover, differences in oligomer abundances for SP mutants (P4A, P2,4A, G9P, and P2,4A/G9P) provide evidence that oligomerization facilitated by TMAO is sensitive to the cis/trans orientation of residues at positions 2, 4, and 9.

Liposomes, which encapsulate drugs into an inner aqueous core and demonstrate high drug-loading capacity, have attracted considerable interest in the field of drug delivery. Herein, the encapsulation processes for amphiphilic copolymers within liposomes have been investigated systematically to enhance the encapsulation capacity and optimize the structures using dissipative particle dynamics simulations. The results indicate that the physicochemical properties of lipids, receptors, and amphiphilic copolymers collectively determine the encapsulation behaviors of liposomes. Adjusting the hydrophobic interaction between hydrophobic tails of lipids (receptors) and hydrophobic blocks of copolymers, along with modulating the specific interaction between ligands and the functional head groups of receptors, can lead to various encapsulation capacities. Significantly, a medium hydrophobic interaction strength or a strong specific interaction is conducive to achieving a higher degree of encapsulation for amphiphilic copolymers. Furthermore, varying the key parameters, such as the hydrophobic interaction, the specific interaction, as well as the concentrations of lipids and receptors, can induce seven typical aggregate structures: heterogeneous, fully encapsulated, partially encapsulated, saturated-encapsulated, unsaturated-encapsulated, multilamellar, and column-like structures. The final phase diagrams are also constructed to provide a guideline for designing various structures of liposomes encapsulated with amphiphilic copolymers. These results significantly contribute to the illumination of strategies for the rational construction of the self-assembly system that facilitates the efficient encapsulation of amphiphilic copolymers within the inner aqueous core of liposomes, thereby providing valuable insights into the optimal design of liposome carriers for future biomedical applications.

Molecular dynamics (MD) simulations of short-chain alcohols (methanol, ethanol, and 1-propanol) in solution were carried out to examine the orientational disordering (randomizing) of alcohol molecules at the surface under diluted conditions. Recent vibrational sum frequency generation (VSFG) spectroscopy, combined with photoelectron spectroscopy, has successfully measured the disordering structure at low concentrations. The present MD simulations accurately reproduce this observation for the first time. To ensure reliable results through MD simulations, several widely used force field models for water and alcohol, including polarizable models, were examined. This examination involved a comparison of structural and thermodynamic quantities, such as surface density times orientation and surface excess concentration, which were obtained through surface-specific measurements like VSFG spectroscopy and surface tension measurements. It is found that the width of the density profile for alcohol molecules at the surface, along the surface normal, increases as the concentration decreases in the diluted condition, which is consistent with the results obtained from the previous neutron and X-ray grazing incidence reflection experiments. A molecular mechanism explaining the disordering of alcohol molecules with decreasing concentration is also discussed.

In this study, we investigate the quaternary ammonium-based ionic liquid (QAIL), methyltrioctylammonium bis(trifluoromethylsulfonyl)imide, [N₁₈₈₈][TFSI], utilizing small angle neutron scattering (SANS) measurements and polarizable molecular dynamics (MD) simulations to characterize the short- and long-range liquid structure. Scattering structure factors show signatures of three length scales in reciprocal space indicative of alternating polarity (k ∼ 0.44 Å^–1), charge (k ∼ 0.75 Å^–1), and neighboring or adjacent (k ∼ 1.46 Å^–1) domains. Excellent agreement between simulation and experimental scattering structure factors validates various simulation analyses that provide detailed atomistic characterization of the different length scale correlations. The first solvation shell structure is illustrated by obtaining radial, angular, dihedral, and combined distribution functions, where two dominant spatial motifs, N⁺···N^– and N⁺···O^–, compete for optimal packing around the polar head of the [N₁₈₈₈]⁺ cation. Intermediate and long-range structures are governed by the balance between local electroneutrality and octyl chain networking, respectively. By computing the charge-correlation structure factor, S_ZZ, and the spatial extent of the octyl chain network using graph theory, the bulk-phase structure of [N₁₈₈₈][TFSI] is characterized in terms of electrostatic screening and apolar domain formation length scales.

We investigate the self-assembly and dynamics of double hydrophilic block copolymers (DHBCs) composed of densely grafted poly[oligo(ethylene glycol) methacrylate] (POEGMA) and poly(vinyl benzyl trimethylammonium chloride) (PVBTMAC) parent blocks by means of calorimetry, small- and wide-angle X-ray scattering (SAXS/WAXS), and dielectric spectroscopy. A weak segregation strength is evident from X-ray measurements, implying a disordered state and reflecting the inherent miscibility between the host homopolymers. The presence of intermixed POEGMA/PVBTMAC nanodomains results in homogeneous molecular dynamics, as evidenced through isothermal dielectric and temperature-modulated DSC measurements. The intermixed process undergoes a glass transition at a temperature approximately 40 K higher than the vitrification of bulk POEGMA segments, and it shifts to an even higher temperature by increasing the content of the hard block. At temperatures below the intermixed glass transition temperature, the confined POEGMA segments between the glassy intermixed regions contribute to a segmental process featuring (i) reduced glass transition temperature (T_g), (ii) reduced dielectric strength, (iii) broader distribution of relaxation times, and (iv) reduced fragility compared to the POEGMA homopolymer. We also observe two glass transition temperatures of dry PVBTMAC, which we attribute to the backbone and side chain segmental relaxation. To the best of our knowledge, this is the first time in the literature that these glass transitions of dry PVBTMAC have been reported. Finally, this study shows that excellent mixing of the two homopolymers is obtained, and this implies that different properties of this copolymer system can be tailored by adjusting the concentration of each homopolymer.

Complementary X-ray absorption fine structure (XAFS) and Raman spectroscopy studies were conducted on various UCl₃ concentrations in alkali chloride salt compositions. The samples were 5 mol % UCl₃ in LiCl (S1), 5 mol % UCl₃ in KCl (S2), 5 mol % UCl₃ in LiCl–KCl eutectic (S4), 50 mol % UCl₃ in KCl (S5), and 20 mol % UCl₃ in KCl (S6) molar concentrations. Samples were heated to 800 °C and allowed to cool to room temperature with measurements performed at selected temperatures; the highest temperatures showed the most stability and will be primarily referenced for conclusions. The processing and interpretation of the Raman and extended X-ray absorption fine structure (EXAFS) peaks revealed several uranium–oxygen bond lengths and symmetries in the samples before, during, and after heating. Based on published thermodynamic data of similar systems, X-ray absorption fine structure spectroscopy, and identification of Raman peaks, a β variation of α-U₃O₈, typical at room temperature, is the suspected dominant phase of all samples at high temperatures (800 °C). In the existing literature, this β structure of U₃O₈ was synthesized by slow cooling of uranium oxides from 1350 °C. This paper suggests the rapid formation of the compound due to the decomposition of the uranium chlorides or oxychlorides at increasing temperatures and O₂ reaction kinetics.

G-quadruplexes (G4s) are four-stranded structures formed by guanine-rich sequences. While their structures, properties, and applications have been extensively studied, an understanding of their folding processes remains limited. In this study, we investigated the folding of the sequence d[(G₃T₂)₃G₃] in potassium solutions, focusing on the impact of a folding intermediate on the overall folding process. Our results indicate that this sequence eventually folds into a parallel G4 structure, either directly or through an antiparallel conformation intermediate, suggesting the existence of a specific competitive folding process. Detailed kinetic analysis using stopped-flow techniques reveals that the antiparallel conformation forms much faster than the parallel one. This antiparallel G4 slowly converts to the thermodynamically favored parallel topology, thus slowing the overall folding rate. As a result, the formation of the parallel quadruplex via an antiparallel G4 intermediate is slower than the direct process, indicating that this antiparallel conformation negatively impacts the overall folding process in a temperature-dependent manner. Interestingly, sodium was shown to facilitate the conversion from antiparallel to parallel. These analyses highlight the complexity of the G4 folding process, which is crucial for most biological applications.