Charge‐Assisted Halogen Bonding: Donor–Acceptor Complexes with Variable Ionicity

Charge‐assisted halogen bonding is unambiguously revealed from structural and electronic investigations of a series of isostructural charge‐transfer complexes derived from iodinated tetrathiafulvalene and tetracyanoquinodimethane derivatives, (EDT‐TTFI₂)₂(TCNQF_n), n=0–2, which exhibit variable degrees of ionicity. The iodinated tetrathiafulvalene derivative, EDT‐TTFI₂, associates with tetracyanoquinodimethane (TCNQ) and its derivatives of increasing reduction potential (TCNQF, TCNQF₂) through highly directional C? I???N≡C halogen‐bond interactions. With the less oxidizing TCNQ acceptor, a neutral and insulating charge‐transfer complex is isolated whereas with the more oxidizing TCNQF₂ acceptor, an ionic, highly conducting charge‐transfer salt is found, both of 2:1 stoichiometry and isostructural with the intermediate TCNQF complex, in which a neutral–ionic conversion takes place upon cooling. A correlation between the degree of charge transfer and the C? I???N≡C halogen‐bond strength is established from the comparison of the structures of the three isostructural complexes at temperatures from 300 to 20 K, thus demonstrating the importance of electrostatics in the halogen‐bonding interaction. The neutral–ionic conversion in (EDT‐TTFI₂)₂(TCNQF) is further investigated through the temperature dependence of its magnetic susceptibility and the stretching modes of the C≡N groups.     

1H-Pyrazolo[3,4-b]quinolines: Synthesis and Properties over 100 Years of Research

This paper summarises a little over 100 years of research on the synthesis and the photophysical and biological properties of 1H-pyrazolo[3,4-b]quinolines that was published in the years 1911–2021. The main methods of synthesis are described, which include Friedländer condensation, synthesis from anthranilic acid derivatives, multicomponent synthesis and others. The use of this class of compounds as potential fluorescent sensors and biologically active compounds is shown. This review intends to summarize the abovementioned aspects of 1H-pyrazolo[3,4-b]quinoline chemistry. Some of the results that are presented in this publication come from the laboratories of the authors of this review.     

柱塞泵油膜压力分析的高效有限单元法

The paper concerns numerical analysis of pressure distribution of an oil film on the valve plate in the variable height gap of an axial piston pump. The analysis employs the finite element method. For determination of oil pressure variations in the gap, the Reynolds equation, commonly applied in the theory of lubrication, is applied. The equation is solved numerically with the use of self-developed program based on the finite element method. In order to obtain high accuracy of the results, an adaptive mesh refinement based on residual estimations of solution errors is applied. The calculation results are represented as dependent on the geometric and working parameters of the pump.     

Determination of Fe(II) and Zn(II) in Vitrum Prenatal by Ion Chromatography (IC). Comparison with Classical and Derivative Spectrophotometry (D0, D1, and D2) with Metrian,Metriap, Metriarez-γ, and Metidarez-β Dyes and with Atomic Absorption Spectrometry

JPC – Journal of Planar Chromatography – Modern TLC - 3-Mercapto-5-(2′-hydroxynaphthylazo-1′)-1,2,4-triazole (metrian);...     

Exploiting Benzophenone Photoreactivity To Probe the Phospholipid Environment and Insertion Depth of the Cell-Penetrating Peptide Penetratin in Model Membranes

Penetratin (RQIKIWFQNRRMKWKK) enters cells by different mechanisms, including membrane translocation, thus implying that the peptide interacts with the lipid bilayer. Penetratin also crosses the membrane of artificial vesicles, depending on their phospholipid content. To evaluate the phospholipid preference of penetratin, as the first step of translocation, we exploited the benzophenone triplet kinetics of hydrogen abstraction, which is slower for secondary than for allylic hydrogen atoms. By using multilamellar vesicles of varying phospholipid content, we identified and characterized the cross-linked products by MALDI-TOF mass spectrometry. Penetratin showed a preference for negatively charged (vs. zwitterionic) polar heads, and for unsaturated (vs. saturated) and short (vs. long) saturated phospholipids. Our study highlights the potential of using benzophenone to probe the environment and insertion depth of membranotropic peptides in membranes.     

Analysis of chaotic non-isothermal solutions of thermomechanical shape memory oscillators

Shape memory materials exhibit strong thermomechanical coupling, so that temperature variations occur during mechanical loading and unloading. In previous works the nonlinear dynamics of pseudoelastic oscillators subject to an harmonic force has been studied and the possibility of non-regular chaotic responses has been thoroughly documented. Instead of the standard Lyapunov exponent treatment, the statistical 0–1 test based on the asymptotic properties of a Brownian motion chain was successively applied to reveal the chaotic nature of trajectories in the special case in which temperature variations were neglected. In this work, the 0–1 test is applied to fully non-isothermal trajectories. To improve its reliability the test has been applied to the time-histories of maxima and minima of each trajectory, in each component. The obtained results have been validated and confirmed by the corresponding Fourier spectra. Non-regular solutions with different levels of chaoticity have been analyzed and their qualitative difference is reflected by the different values to which the control parameter K asymptotically converge.     

Self-assembling mini cell-penetrating peptides enter by both direct translocation and glycosaminoglycan-dependent endocytosis

A small library of cell-penetrating peptides (CPPs) containing a minimized cationic domain and a lipophilic domain of different size was studied. CPPs that could self-assemble were found to enter cells more efficiently, triggering a glycosaminoglycan-dependent pathway.     

Inversion polynomials for 321-avoiding permutations

We prove a generalization of a conjecture of Dokos, Dwyer, Johnson, Sagan, and Selsor giving a recursion for the inversion polynomial of 321-avoiding permutations. We also answer a question they posed about finding a recursive formula for the major index polynomial of 321-avoiding permutations. Other properties of these polynomials are investigated as well. Our tools include Dyck and 2-Motzkin paths, polyominoes, and continued fractions.     

Towards a new family of photoluminescent organozinc 8-hydroxyquinolinates with a high propensity to form noncovalent porous materials

We report on investigations of reactions of tBu(2)Zn with 8-hydroxyquinoline (q-H) and the influence of water on the composition and structure of the final product. A new synthetic approach to photoluminescent zinc complexes with quinolinate ligands was developed that allowed the isolation of a series of structurally diverse and novel alkylzinc 8-hydroxyquinolate complexes: the trinuclear alkylzinc aggregate [tBuZn(q)](3) (1(3)), the pentanuclear oxo cluster [(tBu)(3)Zn(5)(μ(4) -O)(q)(5)] (2), and the tetranuclear hydroxo cluster [Zn(q)(2)](2)[tBuZn(OH)](2) (3). All compounds were characterized in solution by (1)H NMR, IR, UV/Vis, and photoluminescence (PL) spectroscopy, and in the solid state by X-ray diffraction, TGA, and PL studies. Density functional theory calculations were also carried out for these new Zn(II) complexes to rationalize their luminescence behavior. A detailed analysis of the supramolecular structures of 2 and 3 shows that the unique shape of the corresponding single molecules leads to the formation of extended 3D networks with 1D open channels. Varying the stoichiometry, shape, and supramolecular structure of the resulting complexes leads to changes in their spectroscopic properties. The close-packed crystal structure of 1(3) shows a redshifted emission maximum in comparison to the porous crystal structure of 2 and the THF-solvated structure of 3.