Structural equilibrium (S=0) ⇄ (S=1)and inversion of the configuration of the seven-membered saturated metal-containing ring in four-coordinate pyrazolealdiminate metal chelates of nickel(II) based on tetradentate ligands

¹H and¹³C NMR, x-ray structural analysis, and magnetic moment measurements have shown that in 5-thio(seleno)pyrazolealdiminate complexes of nickel(II) based on tetradentate ligands containing the fragment, with n=2, flattening of the chelate unit takes place in solution and in the solid state. A similar structure in which the diamine metal-containing ring has the twist-chair conformation is observed for the crystals of the complexes with n=4. For the complexes with n=4 in solution at a temperature below –50°C, rapid (on the NMR time scale) interconversion of the flattened (P) (S=0) and pseudotetrahedral (T) (S=1) structures is observed, not accompanied by inversion of the tetrahedral configuration of the metal atom. At temperatures above –50°C, in addition to the low-barrier reactions (T) (P), conversion of the seven-membered saturated metal-containing ring and inversion of the tetrahedral configuration of the Ni atom with activation barriers of 48–51 kJ/mole are observed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 327–335, February, 1990.     

Phototropism: a "simple" physiological response modulated by multiple interacting photosensory-response pathways

Phototropism is the process by which plants reorient growth of various organs, most notably stems, in response to lateral differences in light quantity and/or quality. The ubiquitous nature of the phototropic response in the plant kingdom implies that it provides some adaptive evolutionary advantage. Upon visual inspection it is tempting to surmise that phototropic curvatures result from a relatively simple growth response to a directional stimulus. However, detailed photophysiological, and more recently genetic and molecular, studies have demonstrated that phototropism is in fact regulated by complex interactions among several photosensory systems. At least two receptors, phototropin and a presently unidentified receptor, appear to mediate the primary photoreception of directional blue light cues in dark-grown plants. PhyB may also function as a primary receptor to detect lateral increases in far-red light in neighbor-avoidance responses of light-grown plants. Phytochromes (phyA and phyB at a minimum) also appear to function as secondary receptors to regulate adaptation processes that ultimately modulate the magnitude of curvature induced by primary photoperception. As a result of the interactions of these multiple photosensory systems plants are able to maximize the adaptive advantage of the phototropic response in ever changing light environments.     

Water in carbon nanotubes: adsorption isotherms and thermodynamic properties from molecular simulation

Grand canonical Monte Carlo simulations are performed to study the adsorption of water in single-walled (6:6), (8:8), (10:10), (12:12), and (20:20) carbon nanotubes in the 248-548 K temperature range. At room temperature the resulting adsorption isotherms in (10:10) and wider single-walled carbon nanotubes (SWCNs) are characterized by negligible water uptake at low pressures, sudden and complete pore filling once a threshold pressure is reached, and wide adsorption/desorption hysteresis loops. The width of the hysteresis loops decreases as pore diameter narrows and it becomes negligible for water adsorption in (8:8) and (6:6) SWCNs. Results for the isosteric heat of adsorption, density profiles along the pore axis and across the pore radii, order parameter across the pore radii, and x-ray diffraction patterns are presented. Layered structures are observed when the internal diameter of the nanotubes is commensurate to the establishment of a hydrogen-bonded network. The structure of water in (8:8) and (10:10) SWCNs is ordered when the temperature is 298 and 248 K, respectively. By simulating adsorption isotherms at various temperatures, the hysteresis critical temperature, e.g., the lowest temperature at which no hysteresis can be detected, is determined for water adsorbed in (20:20), (12:12), and (10:10) SWCNs. The hysteresis critical temperature is lower than the vapor-liquid critical temperature for bulk Simple Point Charge-Extended (SPCE) water model.     

Novel heterocycles. 6. The condensation of ethyl o-fluorobenzoyl acetate with cyclic imino ethers

The reaction between ethyl o-fluorobenzoylacetate and cyclic imino ethers is described. The products, the corresponding 1,2-fused quinolines ( 13a-17a ), were isolated in good yields. In one instance the uncyclized condensation intermediate 18 was isolated and characterized.     

Diazadiphosphetidine. VIII. Weitere Diazadiphosphetidin-oxide und ein -oxid-sulfid

Diazadiphosphetidines. VIII. Further Diazadiphosphetidine Oxides and an Oxide Sulfide Synthesis and properties of 1,3-dimethyl-2-phenyl-4-diethylamino-1,3,2,4-diazadiphosphetidine-2-oxide ( II ), 1,3-dimethyl-2-diethylamino-4-phenyl-1,3,2,4-diazadiphosphetidine-2-sulfide-4-oxide ( III ), and 1,3-dimethyl-2,4-diphenyl-1,3,2,4-diazadiphosphetidine-2,4-dioxide ( V ) are reported.     

Protection of immobilized sulfhydryl groups against autooxidation by alterations in their microenvironment

Immobilized sulfhydryl groups were prepared by partial thiolation of NH₂-glass beads. The microenvironment of the immobilized SH groups was varied by different chemical modifications of neighboring NH₂ groups. Introduction of a strong charge in the surroundings of immobilized sulfhydryls results in their dramatic stabilization against autooxidation. This effect is due to the salting of O₂ from the surface microlayer of the thiolated beads.     

Thermally induced ortho-metalation of dicarbomethoxyacetylenebis(triphenylphosphine)platinum

Heating a toluene solution of dicarhomethoxyacetylenebis(triphenylphosphine)platinum(0) at 130°C gives the ortho-metalated complex (Ph₃P)(Ph₂$\text{PC}{}_6\text{H}{}_4\text{)P}$t-trans-(COOMe)CCHCOOMe.     

Use of the paramagnetic shift agent Eu(DPM)3 for studying the structure and stereochemistry of conferol and conferone

Summary A spectrophotometric method is proposed for determining the content of aspidin in a crystalline powder and in the rhizomes of the fernsDryopteris spinulosa (M),D. phegopteris (L.), andD. fragrans (L.) Schott.All-Union Scientific-Research Institute for Medicinal Plants. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 684–687, November–December, 1970.     

Delocalization resonance energy of the allylic radical from the geometrical isomerization of hexa-1,3,5-trienes

Thermal cis, trans geometrical isomerization theoretically involves a 90° twisted, singlet diradical-like transition state which may serve as a base for the examination of structural perturbations. Although thermal rearrangement of hexa-1, trans-3,5-triene (and all-trans octa-2,4,6-triene) to the cis isomer cannot be followed directly owing to subsequent cyclization and 1,5 hydrogen shifts, activation parameters for disappearance have been determined. Experimental complications and mechanistic uncertainties which make interpretation difficult are removed in the bicyclic hexatriene, cyclopentenylidenecyclopentene. These geometrical isomers undergo uncomplicated thermal cis, trans isomerization in vessels of lead-potash glass: log k₁ = 12·03±0·32?41·7±0·8/(0·004575T_abs). Extraction of a value for allylic delocalization energy from the behavior of hexa-1, trans-3,5-triene [log k₁ = 12·91 ± 0·47?44·3±1·2/(0·004575 T_abs)] requires corrections of the Dewar-Schmeising type for changes in hybridization of the σ bonds. Depending on whether ethylene or trans-butene is taken as standard, values of 12·2 and 13·1 kcal/mol are obtained (estimated uncertainty ± 2 kcal/mol).