Synthesis and Strong Solvatochromism of Push-Pull Thienylthiazole Boron Complexes

The solvatochromic behavior of two donor-π bridge-acceptor (D-π-A) compounds based on the 2-(3-boryl-2-thienyl)thiazole π-linker and indandione acceptor moiety are investigated. DFT/TD-DFT calculations were performed in combination with steady-state absorption and emission measurements, along with electrochemical studies, to elucidate the effect of two different strongly electron-donating hydrazonyl units on the solvatochromic and fluorescence behavior of these compounds. The Lippert–Mataga equation was used to estimate the change in dipole moments (Δµ) between ground and excited states based on the measured spectroscopic properties in solvents of varying polarity with the data being supported by theoretical studies. The two asymmetrical D-π-A molecules feature strong solvatochromic shifts in fluorescence of up to ~4300 cm⁻¹ and a concomitant change of the emission color from yellow to red. These changes were accompanied by an increase in Stokes shift to reach values as large as ~5700–5800 cm⁻¹. Quantum yields of ca. 0.75 could be observed for the N,N-dimethylhydrazonyl derivative in nonpolar solvents, which gradually decreased along with increasing solvent polarity, as opposed to the consistently reduced values obtained for the N,N-diphenylhydrazonyl derivative of up to ca. 0.20 in nonpolar solvents. These two push–pull molecules are contrasted with a structurally similar acceptor-π bridge-acceptor (A-π-A) compound.     

Solid-state molecular organization and solution behavior of methane-1,1-diphosphonic acid derivatives of heterocyclic amines: the role of the topochemical ring modification and the intramolecular hydrogen bonds in monosubstituted piperid-1-ylmethane-1,1-diphosphonic acids

The crystal structures of 3-methylpiperid-1-ylmethane-1,1-diphosphonic (2), 4-methylpiperid-1-ylmethane-1,1-diphosphonic (3), 2-ethylpiperid-1-ylmethane-1,1-diphosphonic (4), and 2-methylpiperid-1-ylmethane-1,1-diphosphonic (5) acids have been determined and are discussed with respect to their molecular organization and crystal-packing preferences. The chair conformation, predominant also in solution, favors equatorial positioning of the bulky substituents of the heterocyclic N and C atoms. The molecular geometry also provides access to intramolecular hydrogen-bond formation between the axial protons located on the nitrogen atoms, as well as the carbon atoms closest to it, and phosphonic/phosphonate oxygen atoms. The molecules preferably arrange in monolayers, observed in all crystals with an exception of 3. The layers are held in place in the third direction through van der Waals interactions. The analysis of two-dimensional hydrogen-bonded networks is concentrated on revealing how the substituent's topology of the molecule affects the solid-state organization in well-defined structures and is aimed at unraveling the consequences and the possible conformational changes by stepwise network disruption upon crystal dissolution in water. The solution NMR studies are focused on revealing the role that the topochemistry of the substituent plays for the stereodynamics in 2-5. It is demonstrated that in contrast to piperid-1-ylmethane-1,1-diphosphonic acid (1), in which the ring inversion/rotation around the C-N bond concerted with the N-H...O hydrogen-bond breaking/formation process leads to a mixture of two interconverting conformers, the concerted N-H...O breaking/rotation/N-H...O formation process in 2 and 3 allows for a predominance of one conformer in solution. However, placement of a substituent at 2-position in the ring hampers the rotation around the C-N bond; this makes 4 and 5 significantly less flexible relative to compounds 1-3. In addition, both compounds 4 and 5 are proved to exist as a mixture of two conformers, the equilibrium of which in acidic solution is shifted towards the conformer found in solid state. In alkaline solutions of 4 and 5, the equilibrium is shifted towards the conformer that is forced by the flipping of the heterocyclic ring. These results correlate well with recently documented differences in the biological potency of this group of compounds.     

The alpha-helix folds more rapidly at the C-terminus than at the N-terminus

The helix-coil dynamics of different sections of an alpha-helical model peptide were observed separately by nanosecond temperature jump experiments with IR detection on a series of isotopically labeled peptides. The results show that the helix-coil dynamics of the alpha-helical C-terminus are faster than those of the N-terminus.     

Investigation of the electrokinetic properties of paraffin suspension. 2. In cationic and anionic surfactant solutions

Electrical phenomena at nonionogenic hydrophobic surfaces (solid or liquid) in water, electrolyte, and/or surfactant solutions still attract research. In part 1 of this paper we described the electrokinetic behavior of paraffin wax suspension in water and electrolyte solutions (NaCl or LaCl3). On the basis of the latest data of water structure near hydrophobic surfaces it was concluded that immobilized water dipoles at the interface can play an essential role in the zeta potential formation. In this paper were investigated the zeta potentials of paraffin wax in cationic surfactants cetyltrimethylammonium bromide, C16H33(CH3)3NBr, and octadecyltrimethylammonium chloride, C18H37(CH3)3NCl, and anionic surfactant sodium dodecyl sulfate, C12H25SO4Na. Also changes in wettability of the paraffin surface due to the surfactant's adsorption were studied via wetting contact angle measurements and calculation of the surface free energy. It was concluded that at a low surfactant concentration (10(-6) M) the water dipole structure still contributes to the zeta potential, but at a higher one the zeta potential is determined by the surfactant molecules' adsorption. A special role of OH- ions is also clearly seen. Moreover, a functional relationship was found between the surface free energy of the surfactant-covered paraffin surface and the zeta potential.     

Phenol adsorption on closed carbon nanotubes

We present the results of systematic studies of phenol adsorption on closed commercially available, unmodified carbon nanotubes. Phenol adsorption is determined by the value of tube-specific surface area, the presence of small amount of surface groups influence adsorption only in very small amount. Phenol can be applied as a probe molecule for comparative analysis of tube surface areas. Tube curvature influences adsorption from solution, i.e., we observe increasing adsorption energy (and slower desorption process) with the decrease in tube curvature. This is in full accordance with molecular simulation results.     

Electron localization function and electron localizability indicator applied to study the bonding in the peroxynitrous acid HOONO

The ground‐state electronic structure of peroxynitrous acid (HOONO) and its singlet biradicaloid form (HO ··· ONO) have been studied using topological analysis of the electron localization function (ELF), together with the electron localizability indicator (ELI‐D), at the DFT (B3LYP, M05, M052X, and M06), CCSD, and CASSCF levels. Three isomers of HOONO (cis‐cis, cis‐perp, and trans‐perp) have been considered. The results show that from all functionals applied, only B3LYP yields the correct geometrical structure. The ELF and ELI‐D‐topology of the O? O and central N? O bonds strongly depends on the wave function used for analysis. Calculations carried out at CAS (14,12)/aug‐cc‐pVTZ//CCSD(T)/aug‐cc‐pVTZ level reveal two bonds of the charge‐shift type: a protocovalent N? O bond with a basin population of 0.82–1.08e, and a more electron depleted O? O bond with a population of 0.66–0.71e. The most favorable dissociation channel (HOONO → HO + ONO) corresponds to breaking of the most electron‐deficient bond (O? O). In the case of cis‐ and trans‐HO ··· ONO, the ELF, ELI‐D, and electron density fields results demonstrate a closed‐shell O ··· O interaction. The α‐spin electrons are found mainly (0.64e) in the lone pairs of oxygen V_{i = 1,2} (O) from the OH group. The β‐spin electrons are delocalized over the ONO group, with the largest concentration (0.34e) on the lone pair of nitrogen V(N). © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011     

Application of thermovision for estimation of the optimal and safe parameters of the whole body cryotherapy

Exposure to the extreme low temperatures, ranging between ?60 and ?140 °C, has many beneficial effects on the human body what is exploited for example in sport medicine, for treatment of locomotory system diseases or even some psychiatric disorders. To insure the safe treatment in a cryochamber, careful planning of the procedure and proper qualification of patients, is required. Cardiovascular system, especially skin vasculature plays the major role of the body response to the extreme cold. The changes in skin blood flow are reflected in changes of the temperature distribution. Therefore, the thermal imaging, which allows to analyze the temperature distribution on the human body, may be successfully exploited to examine the influence of extremely low temperatures on the skin vascular system. The aim of this work was to examine the temperature, blood pressure, and heart rate changes after the whole body cryotherapy in healthy subjects to determine the safety conditions of the treatment. 480 healthy students of the Wroc?aw University School of Physical Education were divided into two groups (each 240 persons). All subjects were exposed for 1–3 min to the extremely low temperatures: ?60, ?100, ?120, and ?140 °C. In one group, the thermograms were recorded before and 5 and 30 min after the cryotherapy by means of ThermoVision A20 M thermal camera. In the other one, heart rate and blood pressure were measured before and 5 min after the cryotherapy. It was demonstrated that 3-min exposure in the cryochamber and the temperature ?120 °C are the optimal and safe cryotherapy parameters.