Structure of the Active Nanocomplex of Antiviral and Anti-Infectious Iodine-Containing Drug FS-1

Chromatographic analysis shows that the ionic nanostructured complex of the FS-1 drug contains nanocomplexes of α-dextrin with a size of ~40–48 Å. Based on good agreement between the UV spectra of the model structures and the experimental spectrum of the FS-1 drug, the structure of the active FS-1 nanocomplex is proposed. The structure of the active centers of the drug in the dextrin ring was calculated using the quantum-chemical approach DFT/B3PW91. The active centers, i.e., a complex of molecular iodine with lithium halide (I), a binuclear complex of magnesium and lithium containing molecular iodine, triiodide (II), and triiodide (III), are located inside the dextrin helix. The polypeptide outside the dextrin helix forms a hydrogen bond with dextrin in Complex I and coordinates the molecular iodine in Complex II. It is revealed that the active centers of the FS-1drug can be segregated from the dextrin helix and form complexes with DNA nucleotide triplets. The active centers of the FS-1 drug are only segregated on specific sections of DNA. The formation of a complex between the DNA nucleotide and the active center of FS-1 is a key stage in the mechanisms of anti-HIV, anti-coronavirus (Complex I) and antibacterial action (Complex II).

On-the-Fly Ring-Polymer Molecular Dynamics Calculations of the Dissociative Photodetachment Process of the Oxalate Anion

The dissociative photodetachment dynamics of the oxalate anion, C2O4H− + hν → CO2 + HOCO + e−, were theoretically studied using the on-the-fly path-integral and ring-polymer molecular dynamics methods, which can account for nuclear quantum effects at the density-functional theory level in order to compare with the recent experimental study using photoelectron–photofragment coincidence spectroscopy. To reduce computational time, the force acting on each bead of ring-polymer was approximately calculated from the first and second derivatives of the potential energy at the centroid position of the nuclei beads. We find that the calculated photoelectron spectrum qualitatively reproduces the experimental spectrum and that nuclear quantum effects are playing a role in determining spectral widths. The calculated coincidence spectrum is found to reasonably reproduce the experimental spectrum, indicating that a relatively large energy is partitioned into the relative kinetic energy between the CO2 and HOCO fragments. This is because photodetachment of the parent anion leads to Franck–Condon transition to the repulsive region of the neutral potential energy surface. We also find that the dissociation dynamics are slightly different between the two isomers of the C2O4H− anion with closed- and open-form structures.

Improving 1-propanol Force Field: a New Methodology

A new force field for 1-propanol, in the united and all atom models, has been obtained by combining two different empirical methodologies. The first was developed by scaling atom charges, and Lennard-Jones parameters to fit the dielectric constant, surface tension, and density ((2018) J. Chem. Theory Comput. 14:5949-5958). The second methodology consists of moving these parameters and together with the bond distance to obtain the liquid-vapor phase diagram of the CO2 molecule ((1995) J. Phys. Chem. 99:12021-12024). The last methodology is used to obtain the self-diffusion coefficient, which was not considered in the first one. With this new methodology, the experimental density, dielectric constant, surface tension, and self-diffusion coefficient at ambient temperature could be achieved. Furthermore, we show the temperature dependence of the aforementioned properties. The static structure factors are in accordance with the experimental spectrum. Solubility is increased to the experimental value for the united atom model after applying this methodology and for all atom scheme, the experimental solubility value is maintained.

Anharmonic DFT Study of Near-Infrared Spectra of Caffeine: Vibrational Analysis of the Second Overtones and Ternary Combinations

Anharmonic quantum chemical calculations were employed to simulate and interpret a near-infrared (NIR) spectrum of caffeine. First and second overtones, as well as binary and ternary combination bands, were obtained, accurately reproducing the lineshape of the experimental spectrum in the region of 10,000–4000 cm−1 (1000–2500 nm). The calculations enabled performing a detailed analysis of NIR spectra of caffeine, including weak bands due to the second overtones and ternary combinations. A highly convoluted nature of NIR spectrum of caffeine was unveiled, with numerous overlapping bands found beneath the observed spectral lineshape. To properly reflect that intrinsic complexity, the band assignments were provided in the form of heat maps presenting the contributions to the NIR spectrum from various kinds of vibrational transitions. These contributions were also quantitatively assessed in terms of the integral intensities. It was found that the combination bands provide the decisively dominant contributions to the NIR spectrum of caffeine. The first overtones gain significant importance between 6500–5500 cm−1, while the second overtones are meaningful in the higher wavenumber regions, particularly in the 10,000–7000 cm−1 region. The obtained detailed band assignments enabled deep interpretation of the absorption regions of caffeine identified in the literature as meaningful for analytical applications of NIR spectroscopy focused on quantitative analysis of caffeine content in drugs and natural products.

The Spectrum of Crystallographic Misorientations of Intercrystalline Boundaries for BCC-HCP Phase Transformation in Additively Manufactured Ti-6Al-4V

Electron backscatter diffraction is a modern experimental method for local structure and texture investigation, which makes it possible to establish the presence and types of the various boundaries between the elements of the mesostructure such as low or high angle, special and interphase boundaries. Moreover, this technique can demonstrate the migration of boundaries during structural and phase transformations. This study estimated the possible spectrum of crystallographic misorientations of intercrystalline boundaries in additively manufactured titanium alloy Ti-6Al-4V using orientation microscopy and crystallographic calculations based on Burgers orientation relationship during β→α-transformation. The study has established that the boundaries between grains of α-phase are characterized by the misorientation angles of 11±2 °, 61±5 °, 89±3 °. The majority of high-angle boundaries are characterized by misorientation angles in the range of 57-65 °. The study also ascertained that the experimental spectrum of intercrystalline boundaries in the α-phase reveals the displacive nature of β→α-transformation in titanium alloys.

Local solidification thermal parameters affecting the eutectic extent in Sn-Cu and Sn-Bi solder alloys

Purpose Overall, selection maps about the extent of the eutectic growth projects the solidification velocities leading to given microstructures. This is because of limitations of most of the set of results when obtained for single thermal gradients within the experimental spectrum. In these cases, associations only with the solidification velocity could give the false impression that reaching a given velocity would be enough to reproduce a result. However, that velocity must necessarily be accompanied by a specific thermal gradient during transient solidification. Therefore, the purpose of this paper is to not only project velocity but also include the gradients acting for each velocity. Design/methodology/approach Compilation of solidification velocity, v, thermal gradient, G, and cooling rate, Ṫ, data for Sn-Cu and Sn-Bi solder alloys of interest is presented. These data are placed in the form of coupled growth zones according to the correlated microstructures in the literature. In addition, results generated in this work for Sn-(0.5, 0.7, 2.0, 2.8)% Cu and Sn-(34, 52, 58)% Bi alloys solidified under non-stationary conditions are added. Findings When analyzing the cooling rate (Ṫ = G.v) and velocity separately, in or around the eutectic composition, a consensus cannot be reached on the resulting microstructure. The (v vs. G) + cooling rate diagrams allow comprehensive analyzes of the combined v and G effects on the subsequent microstructure of the Sn-Cu and Sn-Bi alloys. Originality/value The present paper is devoted to the establishment of (v vs. G) + cooling rate diagrams. These plots may allow comprehensive analyses of the combined v and G effects on the subsequent microstructure of the Sn-Cu and Sn-Bi alloys. This microstructure-processing mapping approach is promising to predict phase competition and resulting microstructures in soldering of Sn-Cu and Sn-Bi alloys. These two classes of alloys are of interest to the soldering industry, whereas manipulation of their microstructures is considered of utmost importance for the metallurgical quality of the product.

Experimental spectrum of the cosmic ray variations within rigidity range of 1-20 GV in the Earth’s orbit by the data of AMS-02

For the first time, based on the experimental data of AMS-02, a three-parameter spectrum of variations of ga - lactic cosmic rays was obtained in the range of rigidity 1- 20 GV, to which neutron monitors are most sensitive. It was found that during the period of negative polarity of the solar magnetic field, a power-law spectrum of va - riations is observed with a strong exponential decay in the region of high rigidity. When the polarity changes to positive at the beginning of the new 24th solar cycle, the spectrum of cosmic ray variations becomes purely po- wer-law. The transition to the experimentally obtained spectrum of variations will make it possible to remove a number of uncertainties and increase the accuracy of the analysis of data from the ground network of detectors. This will make it possible to retrospectively obtain fluxes of galactic protons with an average monthly resolution for the period of the space era based on ground-based monitoring.

Multiscale Modeling of Electronic Spectra Including Nuclear Quantum Effects

<div>Theoretical prediction of electronic absorption spectra without input from experiment is no easy feat as it requires addressing all the factors that affect line shapes. In practice, however, the methodologies are limited to treat these ingredients only to a certain extent. Here we present a multiscale protocol that addresses the temperature, solvent and nuclear quantum effects, anharmonicity and reconstruction of the final spectra from the individual transitions. First, QM/MM molecular dynamics is conducted to obtain trajectories of solute-solvent configurations, from which the corresponding quantum corrected ensembles are generated through the Generalized Smoothed Trajectory Analysis (GSTA). The optical spectra of the ensembles are then produced by calculating vertical transitions using TDDFT with implicit solvation. To obtain the final spectral shapes, the stick spectra from TDDFT are convoluted with Gaussian kernels where the half-widths are determined by a statistically motivated strategy. We have tested our method by calculating the UV-vis spectra of a recently discovered acridine photocatalyst in two redox states and evaluated the impact of each step. Nuclear quantization affects the relative peak intensities and widths, which is necessary to reproduce the experimental spectrum. We have also found that using only the optimized geometry of each molecule works surprisingly well if a proper empirical broadening factor is applied. This is explained by the rigidity of the conjugated chromophore moieties of the selected molecules which are mainly responsible for the excitations in the spectra. In contrast, we have also shown that the molecules are flexible enough to feature anharmonicities that impair the Wigner sampling. </div>