Sublimation Properties of α,ω-Diamines Revisited from First-Principles Calculations

Sublimation enthalpies of alkane-α,ω-diamines exhibit an odd-even pattern within their homologous series. First-principles calculations coupled with the quasi-harmonic approximation for crystals and with the conformation mixing model for the ideal gas are used to explain this phenomenon from the theoretical point of view. Crystals of the odd and even alkane-α,ω-diamines distinctly differ in their packing motifs. However, first-principles calculations indicate that it is a delicate interplay of the cohesive forces, phonons, molecular vibrations and conformational equilibrium which governs the odd-even pattern of the sublimation enthalpies within the homologous series. High molecular flexibility of the alkane-α,ω-diamines predetermines higher sensitivity of the computational model to the quality of the optimized geometries and relative conformational energies. Performance of high-throughput computational methods, such as the density functional tight binding (DFTB, GFN2-xTB) and the explicitly correlated dispersion-corrected Møller - Plesset perturbative method (MP2C-F12), are benchmarked against the consistent state-of-the-art calculations of conformational energies and interaction energies, respectively.     

Cyanine-Flavonol Hybrids for Near-Infrared Light-Activated Delivery of Carbon Monoxide

Carbon monoxide (CO) is an endogenous signaling molecule that controls a number of physiological processes. To circumvent the inherent toxicity of CO, light-activated CO-releasing molecules (photoCORMs) have emerged as an alternative for its administration. However, their wider application requires photoactivation using biologically benign visible and near-infrared (NIR) light. In this work, a strategy to access such photoCORMs by fusing two CO-releasing flavonol moieties with a NIR-absorbing cyanine dye is presented. These hybrids liberate two molecules of CO in high chemical yields upon activation with NIR light up to 820 nm and exhibit excellent uncaging cross-sections, which surpass the state-of-the-art by two orders of magnitude. Furthermore, the biocompatibility and applicability of the system in vitro and in vivo are demonstrated, and a mechanism of CO release is proposed. It is hoped that this strategy will stimulate the discovery of new classes of photoCORMs and accelerate the translation of CO-based phototherapy into practice.     

Determination of 5-nitroindazole using silver solid amalgam electrode

Monatshefte für Chemie - Chemical Monthly - The voltammetric behavior of 5-nitroindazole was investigated at polished (p-AgSAE) and at mercury meniscus-modified (m-AgSAE) silver solid amalgam...     

Theoretical Aspects of Hydrolysis of Peptide Bonds by Zinc Metalloenzymes

Activation and reaction energies for four model systems capturing the essential physicochemical features of the hydrolysis of the peptide bond have been calculated at various level of theory, including the presumably accurate CCSD(T) calculations. The models studied covered a part of the spectrum encountered in biological systems: the hydrolysis in the absence of metal ions (represented by formamide and Ala–Ala) and the hydrolysis in the presence of one and two zinc(II) ions, mimicking the active sites of mono‐ and dizinc metallopeptidases, respectively (by using thermolysin and glutamate carboxypeptidase II as the model catalytic systems and formamide as the model substrate). The results obtained using CCSD(T)/def2‐TZVP and CCSD(T)/aug‐cc‐pVTZ calculations were used as the benchmark values to which the set of cheaper methods, such as (RI‐)DFT, (RI‐)MP2, and SCS‐MP2, were referenced. It was shown that deviations of 3–5 kcal mol^?1 (translating to 2–3 orders in reaction constants) with respect to the reference CCSD(T) barriers are frequently encountered for many correlated methods and most of studied DFT functionals. It has been concluded that from the set of wave‐function methods, both MP2 and SCS‐MP2 methods can be recommended for smaller models (measured by the mean absolute deviation of the activation barriers over the four systems studied), whereas among the popular DFT functionals, B3LYP and especially M06‐2X are likely to be reasonable choices for calculating the activation barriers of zinc metallopeptidases. Finally, with the model of glutamate carboxypeptidase II, issues related to the convergence of the calculated barriers with the size of the model system used as the representative of the enzyme active site were addressed. The intricacies related to system truncation are demonstrated, and suggest that the correlated wave‐function methods may suffer from problems, such as intramolecular BSSE, which make their usage for the larger system questionable. Altogether, the presented data should contribute to efforts to understand enzymatic catalysis more deeply and to gain control of the accuracy and deficiencies of the available theoretical methods and computational approaches.     

Phenomenological models of elastic nucleon scattering and predictions for LHC

The hitherto analyses of elastic collisions of charged nucleons involving common influence of Coulomb and hadronic scattering have been based practically on West and Yennie formula. However, this approach has been shown recently to be inadequate from experimental as well as theoretical points of view. The eikonal model enabling to determine physical characteristics in impact parameter space seems to be more pertinent. The contemporary phenomenological models admit, of course, different distributions of collision processes in the impact parameter space and cannot give any definite answer. Nevertheless, some predictions for the planned LHC energy that have been given on their basis may be useful, as well as the possibility of determining the luminosity from elastic scattering.     

Adaptive nonlinear control of a continuous stirred tank reactor

The paper deals with continuous-time nonlinear adaptive control of a continuous stirred tank reactor (CSTR). Control strategy is based on the application of a controller consisting of a linear and a nonlinear part. The static nonlinear part is derived as an inversion and exponential approximation of measured or simulated input-output data. Design of the dynamic linear part is based on an approximation of nonlinear elements in the control loop by a continuous-time external linear model with directly estimated parameters. In the control design procedure, polynomial approach with the pole assignment method was used. The nonlinear adaptive control was tested by simulations on a nonlinear model of a CSTR with a consecutive exothermic reaction.     

Ab-initio calculation of electronic structure of partially inverted manganese ferrite

Electronic structure of manganese ferrite is calculated using the density functional theory. Partially inverted structure with the inversion parameter y=0.0625 is considered, using four different supercells (Mn₁₅Fe)_A[Fe₃₁Mn]_BO₆₄ that differ in relative position of Fe_A and Mn_B. The crystal structure was optimized by minimizing the forces acting on the atoms. The spin magnetic moments m of Mn and Fe ions depend to some extent on their position in the supercell, but we found that in all cases m(Mn_B) is considerably smaller (by approx. one Bohr magneton) than m(Mn_A). This indicates strongly that the formal valence of Mn_B is 3+. Trivalent manganese in an octahedral position is expected to exhibit a Jahn–Teller effect and corresponding analysis was performed. No pronounced localization of the extra electron in the octahedral sublattice that would represent the Fe²⁺ ion was found.