Elucidating the hydrotropism behaviour of aqueous caffeine and sodium benzoate solution through NMR and neutron total scattering analysis.

Hydrotropism is a convenient way to increase the solubility of drugs by up to several orders of magnitude, and even though it has been researched for decades with both experimental and simulation methods, its mechanism is still unknown. Here, we use caffeine/sodium benzoate (CAF-SB) as model system to explore the behaviour of caffeine solubility enhancement in water through NMR spectroscopy and neutron total scattering. 1H NMR shows strong interaction between caffeine and sodium benzoate in water. Neutron total scattering combined with empirical potential structure refinement, a systematic method to study the solution structure, reveals π-stacking between caffeine and the benzoate anion as well as Coulombic interactions with the sodium cation. The strongest hydrogen bond interaction in the system is between benzoate and water, which help dissolve CAF-SB complex and increase the solubility of CAF in water. Besides, the stronger interaction between CAF and water and the distortion of water structure are further mechanisms of the CAF solubility enhancement. It is likely that the variety of mechanisms for hydrotropism shown in this system can be found for other hydrotropes, and NMR spectroscopy and neutron total scattering can be used as complementary techniques to generate a holistic picture of hydrotropic solutions.

Accelerated 3D high-resolution T2-weighted breast MRI with deep learning constrained compressed sensing, comparison with conventional T2-weighted sequence on 3.0 T.

PURPOSE: To evaluate the feasibility of isotropic 3D high-resolution T2-weighted imaging (T2WI) MRI sequences and compare the images reconstructed by integrating artificial intelligence-compressed sensing (AI-CS), compressed sensing (CS), and conventional 2D T2WI sequences for quality. MATERIALS AND METHODS: Fifty-two female patients (ages: 26-80 years) with suspected breast cancer were enrolled. They underwent breast MRI examinations using three sequences: conventional T2WI, CS 3D T2WI, and AI-CS 3D T2WI. Image quality, signal-to-noise ratio (SNR), contrast-to-noise ratio, tumor volume, and maximal tumor diameter were compared using the Friedman test. Image quality was scored on a 5-point scale, with 1 indicating nonassessable quality and 5 indicating excellent quality. Tumor volume and maximal tumor diameter were compared based on AI-CS 3D T2WI (slightly high signal), conventional T2WI, and dynamic contrast-enhanced (DCE) sequences. RESULTS: All three T2WI were successfully performed in all patients. 3D CS and AI-CS were significantly better than conventional T2WI in terms of lesion conspicuity and morphology, structural details, overall image quality, diagnostic information for breast lesions, and breast tissue delineation (P < 0.001). The SNR of conventional T2WI was significantly higher for 3D T2WI sequences. The contrast-to-noise ratio was significantly higher for AI-CS 3D T2WI than for conventional T2WI sequence. There was no significant difference in tumor volume between DCE (8.08 ± 16.51) and AI-CS 3D T2WI (8.25 ± 16.29) sequences and no significant differences in tumor diameter among DCE, AI-CS 3D T2WI, and conventional T2WI sequences. CONCLUSION: Isotropic-resolution 3D T2WI sequences can be acquired using AI-CS while maintaining image quality and diagnostic value, which may pave the way for isotropic 3D high-resolution T2WI for clinical application.

Isotopic evidence for quasi-equilibrium chemistry in thermally mature natural gases.

Natural gas is a key energy resource, and understanding how it forms is important for predicting where it forms in economically important volumes. However, the origin of dry thermogenic natural gas is one of the most controversial topics in petroleum geochemistry, with several differing hypotheses proposed, including kinetic processes (such as thermal cleavage, phase partitioning during migration, and demethylation of aromatic rings) and equilibrium processes (such as transition metal catalysis). The dominant paradigm is that it is a product of kinetically controlled cracking of long-chain hydrocarbons. Here we show that C2+n-alkane gases (ethane, propane, butane, and pentane) are initially produced by irreversible cracking chemistry, but, as thermal maturity increases, the isotopic distribution of these species approaches thermodynamic equilibrium, either at the conditions of gas formation or during reservoir storage, becoming indistinguishable from equilibrium in the most thermally mature gases. We also find that the pair of CO2 and C1 (methane) exhibit a separate pattern of mutual isotopic equilibrium (generally at reservoir conditions), suggesting that they form a second, quasi-equilibrated population, separate from the C2 to C5 compounds. This conclusion implies that new approaches should be taken to predicting the compositions of natural gases as functions of time, temperature, and source substrate. Additionally, an isotopically equilibrated state can serve as a reference frame for recognizing many secondary processes that may modify natural gases after their formation, such as biodegradation.

Pre-nucleation aggregation based on solvent microheterogeneity.

Investigation into pre-nucleation aggregates indicating hydrate formation of caffeine and theophylline in aqueous acetonitrile showed hydrate crystallisation at much lower water fraction than significant solute self-association. Molecular dynamics simulations indicate that the solvent separates on the molecular scale and that solute molecules preferentially localise on the phase interface.

Rapid Evaporation of Water on Graphene/Graphene-Oxide: A Molecular Dynamics Study.

To reveal the mechanism of energy storage in the water/graphene system and water/grapheme-oxide system, the processes of rapid evaporation of water molecules on the sheets of graphene and graphene-oxide are investigated by molecular dynamics simulations. The results show that both the water/graphene and water/grapheme-oxide systems can store more energy than the pure water system during evaporation. The hydroxyl groups on the surface of graphene-oxide are able to reduce the attractive interactions between water molecules and the sheet of graphene-oxide. Also, the radial distribution function of the oxygen atom indicates that the hydroxyl groups affect the arrangement of water molecules at the water/graphene-oxide interface. Therefore, the capacity of thermal energy storage of the water/graphene-oxide system is lower than that of the water/graphene system, because of less desorption energy at the water/graphene-oxide interface. Also, the evaporation rate of water molecules on the graphene-oxide sheet is slower than that on the graphene sheet. The Leidenfrost phenomenon can be observed during the evaporation process in the water/grapheme-oxide system.