1-Alkyl-5-((di)alkylamino) tetrazoles: building blocks for peptide surrogates

An approach to the synthesis of 1-alkyl-5-((di)alkylamino)tetrazoles by nucleophilic substitution in 1-alkyl-5-sulfonyltetrazoles with anions generated from the primary or secondary amines was developed. Tolerance of the method to the presence of some functional groups (i.e., protected amine) in both components of the reaction was demonstrated. Obtained tetrazoles are promising building blocks for the design of peptide surrogates, in particular, for replacement approaches of alkyl urea derivatives.     

Ion-beam modification of track membrane surface

An ion-beam method to modify the track membrane surface is suggested. An ion gun based on a magnetron sputterer is developed. This gun provides ion energies in the range of 5 eV–1 keV, ion current density up to 0.8 mA/cm², and an ion beam aperture of 90 mm. After the track membrane surface has been irradiated by argon ions with an energy of 50–100 eV, the angle of surface-water contact decreases from 65°–75° to 10°–25°. If the irradiating ion energy is 300–800 eV, the angle of contact increases from 65°–75° to 90°–100°.     

Temperature-Dependent Photoluminescence of Silver-Indium-Sulfide Nanocrystals in Aqueous Colloidal Solutions

The temperature dependence of the photoluminescence (PL) intensity of colloidal semiconductor nanocrystals (NCs) makes them an appealing option in bio-sensing applications. Here, we probed the temperature-dependent PL behavior of aqueous glutathione (GSH)-capped Ag−In−S (AIS) NCs and their core/shell AIS/ZnS heterostructures. We show that both core and core-shell materials reveal strong PL quenching upon heating from 10 to 80 °C, which is completely reversible upon cooling. The PL quenching is assigned to the thermally activated dissociation of complexes formed by ligands with the metal cations on the NC surface and the introduction of water into the NC coordination sphere. This unique mechanism of the thermal PL quenching results in a much higher temperature sensitivity of the aqueous colloidal AIS (AIS/ZnS) NCs as compared with previously reported analogs capped by covalently bound ligands. Our results are expected to stimulate further studies on aqueous ternary NCs as colloidal luminescent nano-thermometers applicable for ratiometric temperature sensing.     

Determination of a Homogeneous Strictly Pseudoconvex Surface from the Coefficients of Its Normal Equation

Mathematical Notes -     

Giant thermodynamical optical effect near ferroelastic phase transition point in Cs3Bi2I9 layered crystal

For the first time we have found a new giant thermodynamical optical effect near the ferroelastic phase transition point in Cs₃Bi₂I₉ layered crystal. The effect is appeared as periodical oscillations in time of the reflection coefficient. This phenomenon is caused by the small temperature deviations in thermodynamical system the appearance of which in the reflection spectra is strongly amplified in the ferroelastic phase transition point. The optical oscillations are explained on the base of a model that takes into account the temperature dependence of the refractive index through the order parameter (spontaneous strain) of the crystal.     

Modification of oxidized bitumen with styrene-butadiene-styrene copolymers of various structures

Mechanical and structural-rheological properties of oxidized bitumen modified with styrene butadiene-styrene copolymers side vinyl groups in their butadiene fragment were studied. A comparative analysis of the modified and unmodified bitumen composites was performed.     

Mechanism of the transition between lamellar and gyroid phases formed by a diblock copolymer in aqueous solution

The mechanism of the transition from a lamellar phase to a gyroid phase in an aqueous solution of a diblock copolymer has been studied by time-resolved synchrotron small-angle X-ray scattering. The transition occurs via a metastable perforated lamellar structure. The perforations initially have liquidlike ordering before developing hexagonal packing. The transient phase of irregularly perforated layers is revealed by the development of diffuse scattering peaks, just below the Bragg peaks of the lamellar structure. The diffuse scattering is modeled by Monte Carlo simulations of perforated layers. Following the formation of perforations, Bragg peaks characteristic of a hexagonal structure signal an ordering into a hexagonal lattice (with the concomitant loss of diffuse scattering). Computer simulations based on a dynamic density functional model reproduce these features. The hexagonal perforated lamellar phase is rapidly replaced by the gyroid phase. The domain spacing of the gyroid phase is larger than that of the perforated lamellar structure. The perforated lamellar and gyroid phases coexist for a defined period. The reverse transition from gyroid to lamellae occurs directly, with no transient or metastable intermediates.     

Ultraviolet spectroscopy of pyrene in a supersonic jet and in liquid helium droplets

In a series of experiments devoted to the study of polycyclic aromatic hydrocarbons for astrophysical applications, the S(2)<--S(0) transition of jet-cooled pyrene (C(16)H(10)) at 321 nm has been studied by an absorption technique for the first time. The spectra observed by cavity ring-down spectroscopy closely resemble the excitation spectra obtained earlier by laser-induced fluorescence (LIF) and show the same band clusters arising from the vibronic interaction of S(2) with S(1). We have also investigated pyrene when it was incorporated into 380 mK cold helium droplets. These spectra which were recorded employing LIF and molecular beam depletion spectroscopy are broadened and redshifted by 0.94 nm but retain the essential features of the gas phase spectra.     

Detection of homocysteine and cysteine

At elevated levels, homocysteine (Hcy, 1) is a risk factor for cardiovascular diseases, Alzheimer's disease, neural tube defects, and osteoporosis. Both 1 and cysteine (Cys, 3) are linked to neurotoxicity. The biochemical mechanisms by which 1 and 3 are involved in disease states are relatively unclear. Herein, we describe simple methods for detecting either Hcy or Cys in the visible spectral region with the highest selectivity reported to date without using biochemical techniques or preparative separations. Simple methods and readily available reagents allow for the detection of Cys and Hcy in the range of their physiologically relevant levels. New HPLC postcolumn detection methods for biological thiols are reported. The potential biomedical relevance of the chemical mechanisms involved in the detection of 1 is described.     

Solvent effects on optically detected magnetic resonance in triplet spin labels

We have calculated solvent effects on the zero-field splitting (ZFS) constants induced by electron spin–spin coupling (SSC) in the low-lying triplet states of azaaromatic molecules in solutions using multiconfiguration self-consistent-field wave functions and the polarizable continuum model. The second-order spin–orbit coupling (SOC) contribution to the splitting of the ^3* states is found to be almost negligible, and the calculations therefore provide a good estimate of the ZFS parameters and their solvent dependence based only on the electron spin–spin coupling expectation values. The correlation between the shift in the ZFS and the phosphorescence frequency that has been observed in optically detected magnetic resonance experiments in low-temperature glasses is supported by our direct SSC calculations without taking SOC into account. This makes it possible to distinguish between the two theories that earlier were proposed to explain the inhomogeneous broadening of triplet state spectra, and discard the one that is exclusively based on the SOC-induced mixing of the singlet and triplet states.Contribution to the Jacopo Tomasi Honorary IssueAcknowledgments. This work was supported (B. M.) by the Swedish Royal Academy of Science (KVA). This work was also supported by the Norwegian Research Council through a grant of computer time from the Program for Supercomputing. We are grateful to B. Schimmelpfenning for his valuable assistance in the computations.