Terpenoids ofPinus funebris

The complete chemical composition of the oleoresin of the Chinese pine growing in the Far East has been studied. It has been shown that the main components of the monoterpenes are -pinene, -phellandrene, and -terpineol. The sesquiterpenes contain longifolene and compounds related to it. The oleoresin of the Chinese pine is distinguished by a high content of diterpene cembrane compounds. Among the resin acids, dehydroabietic acid predominates (42.4%).Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 444–448, July–August, 1984.     

Temperature and concentration effects on supramolecular aggregation and phase behavior for poly(propylene oxide)-b-poly(ethylene oxide)- b-poly(propylene oxide) copolymers of different composition in aqueous mixtures, 1

The phase behavior (temperature vs composition) and microstructure for the two binary systems Pluronic 25R4 [(PO)19(EO)33(PO)19]-water and Pluronic 25R2 [(PO)21(EO)14(PO)21]-water have been studied by a combined experimental approach in the whole concentration range and from 5 to 80 degrees C. The general phase behavior has been identified by inspection under polarized light. Precise phase boundaries have been determined by analyzing 2H NMR line shape. The identification and microstructural characterization of the liquid crystalline phases have been achieved using small-angle X-ray scattering (SAXS). The isotropic liquid solution phases have been investigated by self-diffusion measurements (PGSE-NMR method). 25R2 does not form liquid crystals and is miscible with water in the whole concentration range; with increasing temperature, the mixtures split into water-rich and a copolymer-rich solutions in equilibrium. 25R4 shows rich phase behavior, passing, with increasing copolymer concentration, from a water-rich solution to a lamellar and copolymer-rich solution. A small hexagonal phase, completely encircled in the stability region of the water-rich solution, is also present. In water-rich solutions, at low temperatures and low copolymer concentrations, the copolymers are dissolved as independent macromolecules. With increasing copolymer concentrations an interconnected network of micelles is formed in which micellar cores of hydrophobic poly(propylene oxide) are interconnected by poly(ethylene oxide) strands. In copolymer-rich solutions water is molecularly dissolved in the copolymer. The factors influencing the self-aggregation of Pluronic R copolymers (PPO-PEO-PPO sequence) are discussed, and their behavior in water is compared to that of Pluronic copolymers (PEO-PPO-PEO sequence).     

Mass spectrometric fragmentation of saturated six membered heterocyclic systems containing two chalcogen family atoms

The mass spectra of six-membered saturated heterocycles containing oxygen, sulphur, selenium and tellurium in the 1,4-positions have been measured. The differing fragmentation modes have been characterized using high resolution, low voltage and metastable ion scan techniques. The important decomposition reactions of the molecular ions involve elimination of C₂H₄ and CH₂X (X is a chalcogen atom) and formation of [C₂H₄X]⁺ and C₂H₅⁺. The propensities of these reactions vary systematically as a function of the ability of the chalcogen to stabilize a positive charge.     

Atomic force microscopy measurement of the elastic properties of the kidney epithelial cells

Direct interaction force measurements using atomic force microscopy (AFM) were carried out between a silicon nitride tip and renal epithelial cells (Madin-Darby Canine Kidney-MDCK and proximal tubular epithelial cells derived from pig kidneys, LLC-PK1). The approaching (extending) portion of the force/distance curves is considered, and repulsive forces in the long range of 2-3 microm were seen in both MDCK as well as LLC-PK1 cells growing under normal conditions. The repulsive force in the shorter distance range of 50-200 nm was also observed, when cells were damaged exposing the underlying basal membrane. LLC-PK1 cells were more prone to damage than the MDCK cells, hence short-range forces were common in the former and long-range forces in the latter cells. The functional dependence of repulsive force on the indentation depth changes, at small indentation depth the force increases linearly, while at larger indentations the force is a quadratic function of the distance, which is attributed to the elasticity of the membrane and the solid-like response of cells, respectively. The oxalate treatment of cells for 2-4 h gives rise to an increase in the elastic modulus of the cells.     

Reactions of 2-aminooxazoles and 2-aminothiazoles with dienophiles. Isolation of stable diels-alder adducts

Room temperature reaction of 2-aminooxazole 1 and its 4- and 4,5-substituted derivatives, with dimethyl acetylenedicarboxylate gave good yields of Diels-Alder adducts 2 , isolated as stable crystalline compounds. A competing process produced oxazole[3,2-a]pyrimidines 3 , also in good yield. Minor products were also identified. 2-Amino-4-methylthiazole ( 6 ) reacted in a similar manner and gave the Diels-Alder adduct 7 and a thia-zolo[3,2-a]pyrimidine 8 as main products with a lesser amount of a thiazole [3,2-d][1:3]diazepine ( 9 ). The aminooxazoles reacted with olefinic dienophiles to give pyridine derivative, formed by breakdown of the original unstable adducts.     

Identification and characterization of active and inactive species for surface-enhanced resonance Raman scattering

The surface-enhanced resonance Raman scattering (SERRS) activity of a statistically significant number of silver nanoparticles has been studied using a correlated SERRS mapping and transmission electron microscopy (TEM) method. TEM allowed the nature of each entity to be directly identified, and the SERRS activity was obtained from the corresponding SERRS map. Particles in various states of aggregation were analyzed to establish relative activities. It was established that SERRS activity is dependent on the specific batch of colloid tested. By averaging different colloid batches, it was shown that increasing SERRS activity is observed with increasing numbers of particles in the aggregates. By reducing the surface coverage of the particles to the extent that single moieties could be examined optically, the ratio of the relative activities of single particles, dimers, trimers, and larger aggregates was estimated. High-resolution TEM images of a number of active and inactive particles are reported. However, no clear correlation between microstructure and SERRS activity was observed.     

Synthesis of cross linked platinum metal containing polyyne polymers

Reaction of Pt(PⁿBu₃)₂Cl₂ (1) or Pt(AsⁿBu₃₂Cl₂ (2) with stoichiometric amounts of 1,3,5-triethynylbenzene, [1,3,5-(H? C?C? )₃C₆H₃] (3)yields monomeric, [1,3,5-Cl(PⁿBu₃)₂(Pt? C? C? )₃C₆H₃] (4), [1,3,5-(C1)(AsⁿBu₃)₂Pt? C? C? ₃C₆H₃] (5) or polymeric, {1,3,5-[(PⁿBu₃)₂Pt? C?C? ]₃C₆H₃? )ⁿ (6), {1,3,5-[(AsⁿBu₃)₂Pt? C? C? ]₃C₆H₃? }ⁿ (7) complexes. Treatment of (1) with (3) and 2,5-diethynyl-p-xylene,H? C? C? C₆H₂(CH₃)₂? C? C? H (8) in varying molar ratios yields a series of high molecular weight cross linked platinum metal containing polyyne copolymers.     

Supramolecular copper hydroxide tennis balls: self-assembly, structures, and magnetic properties of octanuclear [Cu(8)L(8)(OH)(4)](4+) clusters (HL = N-(2-pyridylmethyl)acetamide)

The self-assembly of supramolecular copper "tennis balls" that possess unusual magnetic properties using a small pyridyl amide ligand is described. Copper(II) complexes of N-(2-pyridylmethyl)acetamide (HL) were synthesized in methanol. In the absence of base, the mononuclear complex [Cu(HL)(2)](ClO(4))(2) (1) was prepared. The structure of 1, determined by X-ray crystallography, contains a copper(II) ion surrounded by bidentate HL ligands coordinated via the pyridyl N atom and the carbonyl O atom in a trans, square planar arrangement. Reactions carried out in the presence of triethylamine resulted in cluster complexes [Cu(8)L(8)(OH)(4)](ClO(4))(4) and [Cu(8)L(8)(OH)(4)](CF(3)SO(3))(4) [2(ClO(4))(4) and 2(OTf)(4), respectively]. The cationic portions of 2(ClO(4))(4) and 2(OTf)(4) are isostructural, containing eight copper(II) ions, eight deprotonated ligands (L(-)), and four mu(3)-hydroxide ligands. The top and bottom halves of the cluster are related by a pseudo-S(4) symmetry operation and are held together by bridging L(-) ligands. Solutions of 2(ClO(4))(4) and 2(OTf)(4), which were shown to contain the full [Cu(8)L(8)(OH)(4)](4+) fragment by electrospray mass spectrometry and conductance experiments, are EPR silent. Magnetic susceptibility measurements for 2(ClO(4))(4) as a function of temperature and magnetic field showed the Cu ions all to exhibit magnetic moments in the range expected for the d(9) configuration. At low temperatures, the magnetization was reduced due to predominantly antiferromagnetic interactions between ions. Analysis showed that partially frustrated interactions among the four Cu ions making up each half of the cluster gave good agreement with the data once a large molecular anisotropy was taken into account, with J(c) = 106 cm(-1), D = 27 cm(-1), and g = 2.17.     

Synthesis, physico-chemical and thermal characteristics of seven and ten coordinated complexes of trivalent lanthanides derived from 4[N-(cinnamalidene)amino]antipyrine semicarbazone and diphenyl sulfoxide

In present studies a new series of twenty four complexes of seven and ten coordinated compounds derived from 4[Ncinnamalidene) amino]antipyrine semicarbazone (CAAPS) as primary ligand and diphenyl sulfoxide (DPSO) as secondary ligand has been reported. All the complexes have the general composition LnX_3.n(CAAPS).DPSO (Ln = La, Pr, Nd, Sm, Gd, Tb, Dy or Ho, X = NCS or ClO₄, n = 2, X = NO₃, n = 1). The compounds have been characterized by elemental analysis, molar conductance, magnetic susceptibility, infrared and electronic spectra. Thermal characteristics were also reported. Based on the data appropriate structures are assigned for these complexes.