Reaction of Tricoordinate Phosphorus Compounds with Pseudohalogens. Scope and Mechanism

Abstract

The selectivity of sulphur, selenium and oxygen removal from pseudohalogens: phosphorus disulphides 1 and 2, diselenides 3 and oxophosphoranesulphenyl chlorides 4 has been investigated. A mechanistic rationalization is proposed to account for sulphur (selenium)/oxygen extrusion variation as a function of substrates structure and reaction conditions.     

The segmental and global dynamics in lamellar microphase-separated poly(styrene-b-isoprene) diblock copolymer studied by H NMR and dielectric spectroscopy

The nuclear magnetic resonance (NMR) and dielectric spectroscopy (DS) methods were used to investigate the segmental and global dynamics in lamellar microphase separated poly(styrene-b-isoprene) (SI) diblock copolymer. For the first time, the susceptibility representation of the NMR relaxation data is applied to the analysis of the molecular dynamics in complex polymer systems like the diblock copolymer. This approach in combination with the frequency-temperature superposition (FTS) allows one to compare directly the NMR and DS data in an extended frequency range providing a unique comprehensive picture of various relaxation processes present in the system studied. The findings of these investigations include structural relaxations of the polyisoprene (PI) and the polystyrene (PS) blocks, a normal mode relaxation of the PI block, and an extra low frequency interfacial relaxation. Special attention has been devoted to influence of the copolymer morphology on the segmental and global dynamics in PI.     

Synthesis of Some Novel N-Substituted Phthalazinone and Pyridopyridazinone Derivatives

Phthalazinone and pyridopyridazinone derivatives 3, 5, and 9 were prepared via reaction ofappropriate lactams 2 and 8 with 2-bromoethylphthalimide, N-tosylaziridine, and N,O-ditosyl derivatives of N-methylethanolamine in a two-step process in the presence of MeONa/MeOH or NaH/dimethylformamide (DMF). Starting compounds 2 and 8 were obtained by reaction of hydrazine hydrate with isoindolinones 1 or azaisoindolinones 6. Selected N-(2-phthalimidoethyl)-phthalazinones were converted into corresponding 2-[2-(methylamino) ethyl]- derivatives in satisfactory yields by treatment with hydrazine.     

Application of 2,4,6-trioxo-pyrimidin-5-ylidene alditols in the synthesis of pyrano[2,3-d]pyrimidines containing a sugar moiety by hetero-Diels–Alder reactions and by conjugate Michael addition–cyclizations

A convenient and efficient procedure for the preparation of 3,4-dihydro-2H-pyran derivatives containing a sugar moiety is described. The reaction sequence is: Knoevenagel condensation of unprotected sugars and CH acids, acetylation of C-glycosides and hetero-Diels–Alder reaction. O-Acetylated 1,3-dimethyl-2,4,6-trioxo-pyrimidin-5-ylidene derivatives were used as new heterodienes in the synthesis of fused uracils—pyrano[2,3-d]pyrimidines with a sugar moiety. Solvent-free hetero-Diels–Alder cycloadditions of O-acetylated pyrimidin-5-ylidene alditols with enol ethers and cyclic enol ether were investigated at room temperature. New, enantiomerically pure cis and trans diastereoisomers of pyrano[2,3-d]pyrimidines and cis–cis, trans–cis diastereoisomers of pyrano[3′,2′:5,6]pyrano[2,3-d]pyrimidines with alditol moiety were obtained. The same pyrimidin-5-ylidene alditols underwent conjugate Michael addition–cyclizations with malononitrile at room temperature to afford optically active diastereoisomers of pyrano[2,3-d]pyrimidine-6-carbonitriles with a sugar moiety.     

Age-Related Carbonylation of Fibrocartilage Structural Proteins Drives Tissue Degenerative Modification

1. Download : Download high-res image (219KB)
2. Download : Download full-size image

     

The electrochemical behavior of PtRu- and Pt-modified zeolite X in alkaline solution

Zeolite NaX was modified by Pt and Pt/Ru nanodispersed metallic clusters. The procedure of impregnation with acetylacetonate salt/acetone solution was applied. Scanning electron microscope analysis confirmed partial zeolite framework destruction. According to energy dispersive X-ray analysis, Pt/Ru ratio in sample was about 1. Electrochemical behavior of PtRu- and Pt-modified zeolites was investigated in alkaline solutions, 5 mM NaOH?+?1 M Na₂SO₄ and 0.1 M NaOH. The shape of cyclic voltammograms of 13XPtRu electrode, recorded in slightly alkaline solution, was greatly affected by the presence of hydrogen that remained in the sample after synthetic procedure. Oxygen reduction reaction (ORR) was investigated in an O₂-saturated aqueous 0.1-M NaOH solution. The obtained Tafel slopes indicated ORR mechanism that involves one-electron discharge-determining step. According to Koutecky–Levich slope, the oxygen reduction reaction followed 4e^? mechanism on both 13XPtRu and 13XPt electrode. The onset of ORR on 13XPtRu electrode was shifted toward more positive potentials in comparison to 13XPt electrode.     

A Raman microspectroscopic study of organic inclusions in “watermelon” tourmaline from the Paprok mine (Nuristan, Afghanistan)

An exceptional mineral specimen, particularly interesting for collectors and researchers, is “watermelon” tourmaline, mined in the Paprok region in Nuristan, Afghanistan. A pale pink core (zone III) is surrounded by a thin, colorless zone (zone II), and a green outer zone (zone I). Differences between zones are clearly seen in the SEM picture, i.e., diversity in the size of constituent forms, and also the presence of inclusions of alien mineral phases which range from a few dozen to a few μm. In the line mapping experiment the Raman spectra were collected from the inner core towards the outer rim. There are observed typical for tourmaline (elbaite) groups of bands: at ca. 3600, 1100, 700, 400 and 250 cm⁻¹. Raman measurements determine the differences in the local chemical composition of particular zones. Interestingly, there is a new band emerging in the outer zone at ca. 840 cm⁻¹, and it could be due to the SiO₄ stretching vibrational modes predisposed by the Fe ion presence in the mineral. The organic inclusions are present in the whole volume of the investigated gem. Organic inclusion content appears to be versatile. Raman spectra confirm the presence of hydrogen sulphide (2610 cm⁻¹), methane (2912 cm⁻¹), ethane (2950 cm⁻¹), and propane (2895 cm⁻¹). In the corresponding bending vibrations region apart from CH₂, CH₃ vibrations and C–O stretching (CO₂) at (1280, 1390 cm⁻¹), characteristic bands are also observed at ca. 1340, 1600 and 1660 cm⁻¹. The last ones possibly mark the evolution of graphitization process occurring from fluid saturated inclusions within condensed ring aromatics (1660 cm⁻¹ band), towards slightly more organized, although still amorphous forms of carbonaceous matter (1340 and 1600 cm⁻¹).     

Freeze vs. Spray Drying for Dry Wild Thyme (Thymus serpyllum L.) Extract Formulations: The Impact of Gelatin as a Coating Material

Freeze drying was compared with spray drying regarding feasibility to process wild thyme drugs in order to obtain dry formulations at laboratory scale starting from liquid extracts produced by different extraction methods: maceration and heat-, ultrasound-, and microwave-assisted extractions. Higher total powder yield (based on the dry weight prior to extraction) was achieved by freeze than spray drying and lower loss of total polyphenol content (TPC) and total flavonoid content (TFC) due to the drying process. Gelatin as a coating agent (5% w/w) provided better TPC recovery by 70% in case of lyophilization and higher total powder yield in case of spray drying by diminishing material deposition on the wall of the drying chamber. The resulting gelatin-free and gelatin-containing powders carried polyphenols in amount ~190 and 53–75 mg gallic acid equivalents GAE/g of powder, respectively. Microwave-assisted extract formulation was distinguished from the others by a higher content of polyphenols, proteins and sugars, higher bulk density and lower solubility. The type of the drying process mainly affected the position of the gelatin-derived -OH and amide bands in FTIR spectra. Spray-dried formulations compared to freeze-dried expressed higher thermal stability as confirmed by differential scanning calorimetry analysis and a higher diffusion coefficient; the last feature can be associated with the lower specific surface area of irregularly shaped freeze-dried particles (151–223 µm) compared to small microspheres (~8 µm) in spray-dried powder.     

Induced magnetic anisotropy in Co-doped Finemet-type nanocrystalline materials

Transverse magnetic anisotropy has been induced in the Fe_14.7Co_58.8Cu₁Nb₃Si_13.5B₉ and Fe_13.8Co₆₅Cu_0.6Nb_2.6Si₉B₉ amorphous ribbons by annealing under an external magnetic field. This anisotropy plays a predominant role, compared to magneto-crystalline and magneto-elastic anisotropies, in forming the magnetic properties and shaping the hysteresis loop. The effect of temperature and time of annealing on the induced magnetic anisotropy and magnetic properties (magnetic permeability, coercivity and power losses) in both alloys was investigated. Under this work, measurements of frequency dependence of the real and imaginary parts of magnetic permeability were made within a frequency range up to 110 MHz. It was found that as a result of magnetic field annealing the Snoek limit increases in both alloys compared to the Co-free Finemet.     

BaHfO3:Ce sintered ceramic scintillators

Raw powders of BaHfO₃:Ce were prepared with modified Pechini process and were calcined in the 650–1700 °C range of temperatures, at different atmospheres – air, vacuum and nitrogen–hydrogen mixture. The powders were converted into sintered ceramics by vacuum sintering. The materials were characterized by XRD, TEM, photoluminescence and radioluminescence spectroscopy. UV-VUV excitation spectra were recorded using synchrotron radiation. Excitation spectra proved that atmosphere of preparation significantly influences the host-to-activator energy transfer, which is the most efficient for materials made in reducing conditions. Also radioluminescence efficacy was found to be superior for materials prepared in such conditions.