Electron spin echo as a tool for investigation of surface structure of finely dispersed fractal solids

The ESE method was successfully used for investigating the texture of the adsorbents and catalysts. Equations were obtained for the kinetics of ESE signal decay due to dipole-dipole interaction between motionless paramagnetic centers distributed uniformly on the fractal surface of solid.

---

, . , , .

     

Determination of cisplatin and related platinum complexes in plasma ultrafiltrate and urine by high-performance liquid chromatography with on-line radioactivity detection

A reversed-phase ion-pair chromatographic method with on-line radioactivity detection for the simultaneous determination of 195mPt-labelled cisplatin and related platinum complexes has been developed. With this system a good resolution of various radiolabelled platinum complexes can be achieved. The detection limit of the radioactivity detector is 10 ng of cisplatin (specific activity of 15 MBq/mg cisplatin) per millilitre of urine or plasma ultrafiltrate. The detector response is independent of both the chemical structure of the platinum complexes and the matrix composition of the samples. This method may serve as a reference system for other high-performance liquid chromatographic systems with less specific and sensitive detectors.     

The rheological similarity of the physical networks of different origin

It has been established that the Newtonian viscosity of solutions of styrene-acrylic acid (4 mol%) copolymers inionomeric form (0–50 mol%) in DMPh is proportional to exp n (n being the degree of neutralization). The principle of temperature-time-concentration superposition is applicable for the dependence of shear modulus on temperature (20–100°), frequency (10^?3–1.5 Hz), decree of neutralization (0–50 mol%) and concentration (15–45 g/dl). These facts can be explained in terms of the rheological similarity of physical networks connected with macromolecular chain entanglements and with salt group interactions. Some details of the model for concentrated polymer solutions are discussed.     

Quantum-chemical investigation of the influence of the vacant orbitals of the heteroatom on the shaping of the electronically excited states and luminescence-spectroscopic properties of triphenylgallium

The electronic structure of the triphenylgallium molecule in the ground and electronically excited states has been calculated in the framework of the CNDO/S-CI method in sp and spd bases. The electron density in the AO's and atoms, the first ionization potential the energies and matrices of the changes in the electron density of the S_n and T_n states, the matrix elements of the spin-orbit coupling operator $$ " align="middle" border="0"> and $$ " align="middle" border="0"> , the intensities and directions of polarization of the S_n S_o and T₂ T_n transitions, and the phosphorescence lifetimes have been calculated. The following spectroscopic parametrization has been proposed for the Ga atom in the sp and spd bases: 1/2(I_s + a_s) = 10.075 eV, 1/2(I_p + A_p) = 4.265 eV, 1/2(I_d + A_d)=0, _Ga ^p =5 eV, _Ga ^d =O, _Ga ^sp =–7 eV, _Ga ^spd =–10 eV, and _s,p,d=1.433. The influence of the d AO's on the shaping of the orbital nature of the S₁ and T₂ states has been analyzed.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 584–590, September–October, 1985.     

Interactions des alcynes avec les complexes carbéniques du tungstène portant une double liaison carbone— carbone: Accès aux dérivés bicyclo[4,1,0] heptaniques par insertion-cyclopropanation

Treatment of VO(acac)₂ with the facial-tridentate organometallic ligand [η-CpCo{P(O)(OEt)₂}₃]^? affords a new binuclear compound [η-CpCo{P(O)(OEt)₂}₃VO(acac)] (I). This compound undergoes protonation with HPF₆ in the presence of 1,10-phenanthroline (phen), or 2,2′-bipyridyl (bipy), to yield binuclear cationic derivatives [η-CpCo{P(O)(OEt)₂}₃VO(phen))]⁺PF₆^? (II), and [η-CpCo{P(O)(OEth)₂}₃VO(bipy)]⁺PF₆^? (III). The X-ray crystal structure determination and full characterization of I has been performed. The catalytic oxygenation and oxygen transfer to 3,5-di-t-butylcatechol in the presence of I, II⁺, or III⁺ complexes is reported.     

Synthesis of nucleosides of substituted 3-hydroxypyrazoles

N-Glucoside analogs of the antibiotic pyrazofurine were obtained by fusion of 3-hydroxy-4-ethoxycarbonylpyrazole with tetra-O-acetyl-ß-D-ribofuranose in the presence of iodine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1512–1514, November, 1981.     

Oxepinamides A-C and fumiquinazolines H--I: bioactive metabolites from a marine isolate of a fungus of the genus Acremonium

Three new oxepin-containing natural products (1-3) and two new fumiquinazoline metabolites (4-5) have been isolated from organic extracts of the culture broth and mycelia of an Acremonium sp., a fungus obtained from the surface of the Caribbean tunicate Ecteinascidia turbinata. The structures of the five compounds were determined through extensive analysis of 1D- and 2D-NMR data, and mass spectrometry. Compound 1 exhibited good anti-inflammatory activity in a topical RTX-induced mouse ear edema assay. Compounds 4 and 5 exhibited weak antifungal activity toward Candida albicans in a broth microdilution assay.     

Formation of intermolecular hydrogen bonds in light-sensitive crystals of C-2′-(o-oxyphenyl)vinyl-N-p-methylphenyl nitrone,C-2′-(2″-oxy-5″-bromophenyl)vinyl-N-p-methylphenyl nitrone,C-2′-(2″-oxy-5″-bromophenyl)-vinyl-N-phenyl nitrone,and C-2′-(o-oxyphenyl)vinyl-n-methyl nitrone

This paper studies the crystal structure of new substituted light-sensitive azomethine N-oxides (nitrones): C-2′-(o-oxyphenyl)vinyl-N-p-methylphenyl nitrone (1), C-2′-(2″-oxy-5″-bromophenyl)vinyl-N-p-methylphenyl nitrone (2), C-2′-(2″-oxy-5″-bromophenyl)-vinyl-N-phenyl nitrone (3), and C-2′-(o-oxyphenyl)vinyl-N-methyl nitrone (4). In contrast to the compounds studied earlier [1, 2], C-2′-(β-oxy-α-naphthyl)vinyl-N-p-methylphenyl nitrone (5), C-2′-(β-oxy-α-naphthyl)vinyl-N-phenyl nitrone (6), C-2′-(o-oxyphenyl) vinyl-N-phenyl nitrone (7), and C-2′-(o-oxyphenyl)vinyl-N-p-bromophenyl nitrone (8), the nitrones studies in this work have anti-rather than syn-orientations of the nitrone and hydroxyl groups. Due to this spatial arrangement of the proton-donating hydroxyl and proton-accepting nitrone groups, molecules in crystals 1–4 are bonded by intermolecular hydrogen bonds (IHB) to form chains but not centrosymmetric dimeric associates (CDA). Two types of chain arrangements were revealed: “head-to-tail” and “head-to-tail, tail-to-head”. It is shown that the introduction of an alkyl substituent instead of an aryl one at the nitrogen atom of the nitrone group in 4 leads to a change in the geometry of the IHB in the H-associate. It is proven that the hydroxyl proton can undergo an intermolecular O→O transfer in the chain of hydrogen bonds in crystals 1–4, which can give rise to photochemical transformations in these crystals. Institute of Chemical Physics in Chernogolovka, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 37, No. 2, pp. 349–362, March–April, 1996. Translated by L. Smolina     

Application of Mass Spectrometry and Chromatography–Mass Spectrometry in Drug Analysis

The review is devoted to the use of mass spectrometry and chromatography–mass spectrometry in various areas of pharmaceutical chemistry. The role of the above techniques in the structural identification of impurities in drug preparations and in the determination of the biotransformation behavior of pharmaceuticals in human and animal bodies is shown. The inactivation of drugs under the action of external factors (oxidation by atmospheric oxygen and the effects of moisture, heat, and light) is illustrated. The use of various ionization techniques and the spectra of metastable ions for determining the structures of components of biologically active substances are exemplified.     

Sorption Concentration of Radiocesium on NaX Zeolite Modified with Cu2[Fe(CN)6]

Sorption of ¹³⁷Cs on NaX zeolite modified with Cu₂[Fe(CN)₆] was studied under dynamic conditions.