Ring Tension Applied to Thiol‐Mediated Cellular Uptake

The objective of the study was to explore the potential of ring tension in cyclic disulfides for thiol‐mediated cellular uptake. Fluorescent probes that cannot enter cells were equipped with cyclic disulfides of gradually increasing ring tension. As demonstrated by flow cytometry experiments, uptake into HeLa Kyoto cells increased with increasing tension. Differences in carbon‐sulfur‐sulfur‐carbon (CSSC) dihedral angles as small as 8° caused significant changes in uptake efficiency. Uptake with high ring tension was better than with inactivated or activated linear disulfides or with thiols. Conversion of thiols on the cell surface into sulfides and disulfides decreased the uptake. Reduction of exofacial disulfides into thiols increased the uptake of transporters with disulfides and inactivated controls with thiols. These results confirm the occurrence of dynamic covalent disulfide‐exchange chemistry on cell surfaces. Mechanistic and colocalization studies indicate that endocytosis does not fully account for this cellular uptake with ring tension.     

Synthesis of diamides from 1,4-benzodioxane-2- and isochroman-1-carboxylic acids

1,4-Benzodioxane-2-carboxylic acid and isochroman-1-carboxylic acid were treated with thionyl chloride, and the resulting acid chlorides reacted with p-aminobenzoic acid in dioxane in the presence of pyridine to produce the corresponding amido acids. The latter were converted into acid chlorides which were brought into reaction with various amines to obtain a number of new diamides.     

Investigation of atomic transitions of cesium in strong magnetic fields by an optical half-wavelength cell

It has been demonstrated that the use of the λ/2 method allows one to effectively investigate individual atomic levels of the D ₂ line of Cs (with the most complicated spectrum among all alkali metals) in strong magnetic fields up to 7 kG. The method is based on strong narrowing of the absorption spectrum (which provides sub-Doppler resolution) of a cesium-filled thin cell with the thickness L equal to a half-wavelength (L = λ/2) of the laser radiation (λ = 852 nm) resonant with the D ₂ line. In particular, the λ/2 method has allowed us to resolve 16 atomic transitions (in two groups of eight atomic transitions each) and to determine their frequency positions, fixed (within each group) frequency slopes, the probability characteristics of the transitions, and other important characteristics of the hyperfine structure of Cs in the Paschen-Back regime. Possible applications are mentioned. Two theoretical models have been implemented. The values of the magnetic field have been indicated at which the models describe the experiment well.     

Splitting of the electromagnetically induced transparency resonance on 85Rb atoms in strong magnetic fields up to the Paschen-Back regime

Electromagnetically induced transparency (EIT) resonance in strong magnetic fields of up to 1.7 kG has been investigated with the use of a 30-??m cell filled with an atomic rubidium vapor and neon as a buffer gas. The EIT resonance in the ?? system of the D₁ line of ⁸⁵Rb atoms has been formed with the use of two narrowband (??1 MHz) 795-nm diode lasers. The EIT resonance in a longitudinal magnetic field is split into five components. It has been demonstrated that the frequencies of the five EIT components are either blue- or red-shifted with an increase in the magnetic field, depending on the frequency ??_P of the probe laser. In has been shown that in both cases the ⁸⁵Rb atoms enter the hyperfine Paschen-Back regime in magnetic fields of >1 kG. The hyperfine Paschen-Back regime is manifested by the frequency slopes of all five EIT components asymptotically approaching the same fixed value. The experiment agrees well with the theory.     

A study of dark resonance splitting for the D 1 line of 87Rb in strong magnetic fields

The process of electromagnetically induced transparency (EIT) is studied using an extremely thin cell with thickness of a vapor column of rubidium atoms L = 794 nm. Wavelengths of resonant laser beams ?? ?? 794 nm. Results of the study of behavior of the EIT resonance (which is also called the ??dark?? resonance) formed in the ?? system of the D ₁ line of ⁸⁷Rb atoms in strong magnetic fields up to 1700 G (0.17 T) are reported for the first time. Three dark resonances are recorded in magnetic fields with induction B < 300 G, two resonances are recorded at B > 650 G, and only one dark resonance is retained at B > 1200 G. A method of the formation of a dark resonance at a given frequency is demonstrated that will allow, under the corresponding conditions, the formation of a dark resonance also at B > 0.2 T. The experimental results are well described by the known theoretical models. Practical applications of these results are indicated.     

Electromagnetically induced transparency and two-photon absorption in the ladder system in thin columns of atomic vapors

Experimental results of the study of processes of electromagnetically induced transparency (EIT) and two-photon absorption (TPA) are presented for the ladder Ξ-system obtained using the 5S-5P-nD, mS system of levels of the ⁸⁵Rb and ⁸⁷Rb atoms with n = 5, 26, and 27 and m = 39 and 48. To perform these studies, a high-temperature optical cell was designed with several regions with the following thicknesses L: 2 mm, 0.7 mm, and the region of 2–6 μm. The advantages of using thin cells over ordinary cells several centimeters thick are demonstrated. It is shown that the EIT resonance parameters for n = 5, 26, and 27 deteriorate insignificantly for thickness down to 700 μm. The TPA is recorded with the cell thickness decreasing down to L = 6 μm. It is shown that using the EIT and TPA processes makes it possible to measure the hyperfine and fine structures of highlying atomic levels. The influence of the cell walls is appreciable in recording the EIT resonances in the system 5S-5P-39S with L = 0.7 mm and in the system 5S-5P-48S with L = 2 mm. Possible applications of the processes studied are indicated.     

Magnetically Induced Anomalous Dichroism of Atomic Transitions of the Cesium D<Subscript>2</Subscript> Line

An alternative treatment of the well-known effect of a decrease in the Morin transition temperature in hematite with a decrease in the size of crystallites to the complete disappearance of the transition for nanoparticles smaller than 20 nm is proposed. In contrast to the standard speculative explanation of this effect in terms of the effect of surface and defectiveness of grains, we suggest that the decisive factor is an increase in the contribution of the shape anisotropy of particles with a decrease in their size, which is responsible for the spread of orientations of the axes of the resulting magnetic anisotropy with respect to the crystallographic axes. Our reasons are confirmed by a numerical analysis of Mössbauer spectra of hematite nanoparticles within the continuous model of magnetic dynamics of an ensemble of antiferromagnetic nanoparticles in the two-sublattice approximation generalized to the existence of weak ferromagnetism (Dzyaloshinskii interaction).     

Linear polymer with hydrogen bonds as a nonequilibrium system

A two-temperature nonequilibrium model of a linear polymer with possible formation of hydrogen bonds between monomers is proposed. A molecule is considered to be in an adiabatic stationary state far from equilibrium. The dependence of the mean-square distance between the chain ends on the number of monomers is calculated with the simplest approach of Flory in case T > Θ.     

Preparation and investigation of rare earth magnesium hexaaluminate solid solutions

Conditions of preparation, by the method of solid state reactions, of rare-earth hexaaluminates RE_1?x?yM_xM’_yMgAl₁₁O₁₉ (RE = La, Sm; M, Mt’ = Gd, Yb, Lu, Y, Sc; x, y = 0, 0.15, 0.3), were investigated. For a number of compositions, high-degree single-phase products were obtained applying multi-step heat treatments in Ar/H₂ atmosphere at 1650–1690°C. Intense (107) and (114) diffraction lines typical for the hexaaluminate phase have been observed in X-ray diffraction patterns. Studies of microstructure and of elemental composition showed that magnesium deficiency on the sample surface may reach some 20%, while composition in the bulk is more homogeneous and close to stoichiometric. Our estimations of structural homogeneity and thermal conductivity show that lanthanum hexaaluminates La_1?x?yM_xM’_yMgAl₁₁O₁₉ with pair additives Gd-Yb, Gd-Y, Y-Yb, Y-Lu, Y-Sc (x = y = 0.15) and samarium hexaaluminates Sm_1?x?yM_xM’_yMgAl₁₁O₁₉ with pair additives Gd-Yb, Y-Yb (x = y = 0.15), as well as Sm_0.7Yb_0.3MgAl₁₁O₁₉, may present interest as thermal barrier coatings.