New study of the stability and of the spectroscopy of the molecular anions NCO- and CNO-

Using highly correlated wave functions, the ground and the low lying excited states of the molecular NCO(-) and CNO(-) anions have been reinvestigated. The stability of the electronic ground state of the two isomers with respect to dissociation and to electron detachment has been checked along the isomerization pathway. The regions of stability of the excited electronic states have been analyzed and identified and it is shown that only the ground state is stable and the corresponding potential energy surface presents three equilibrium positions. The rovibronic spectroscopy of the X (1)Σ(+) state of both NCO(-) and CNO(-) isomers has been determined by a variational approach leading to remarkable agreement with experimental data.     

The energy pump and the origin of the non-equilibrium flux of the dynamical systems and the networks

The global stability of dynamical systems and networks is still challenging to study. We developed a landscape and flux framework to explore the global stability. The potential landscape is directly linked to the steady state probability distribution of the non-equilibrium dynamical systems which can be used to study the global stability. The steady state probability flux together with the landscape gradient determines the dynamics of the system. The non-zero probability flux implies the breaking down of the detailed balance which is a quantitative signature of the systems being in non-equilibrium states. We investigated the dynamics of several systems from monostability to limit cycle and explored the microscopic origin of the probability flux. We discovered that the origin of the probability flux is due to the non-equilibrium conditions on the concentrations resulting energy input acting like non-equilibrium pump or battery to the system. Another interesting behavior we uncovered is that the probabilistic flux is closely related to the steady state deterministic chemical flux. For the monostable model of the kinetic cycle, the analytical expression of the probabilistic flux is directly related to the deterministic flux, and the later is directly generated by the chemical potential difference from the adenosine triphosphate (ATP) hydrolysis. For the limit cycle of the reversible Schnakenberg model, we also show that the probabilistic flux is correlated to the chemical driving force, as well as the deterministic effective flux. Furthermore, we study the phase coherence of the stochastic oscillation against the energy pump, and argue that larger non-equilibrium pump results faster flux and higher coherence. This leads to higher robustness of the biological oscillations. We also uncovered how fluctuations influence the coherence of the oscillations in two steps: (1) The mild fluctuations influence the coherence of the system mainly through the probability flux while maintaining the regular landscape topography. (2) The larger fluctuations lead to flat landscape and the complete loss of the stability of the whole system.     

Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment

Nanomaterials have one dimension <100 nm and possess physico-chemical properties dictated by their unusually small size, large surface area, shape and chemical composition. New properties of nanomaterials have boosted their production and industrial applications in many fields (e.g., microelectronics, catalysis, fuel cells, materials science, textiles, biotechnology and medicine). In biomedical fields, nanomaterials are of the appropriate dimensions to interact with biological matter. However, they may also have negative effects on biological systems. Nanotechnology is a major, innovative, scientific and economic growth area, but the increasing production and use of nanomaterials have led to calls for more information regarding the potential impacts that their release may have on human health and the environment.This review addresses analytical approaches for characterization and quantification of nanomaterials in the environment and recent studies on their occurrence, fate and behavior.     

Isolation and identification of the anti-isohumulones and the anti-acetylhumulinic acids

The anti-isohumulones [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-hydroxy-4-(4-methylpent-3-enoyl)-cyclopentane-1,3-diones] and the anti-acetylhumulinic acids [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-ethanoyl-4-hydroxy-cyclopentane 1,3-diones] have been isolated from an isomerisation reaction mixture of humulone [2-(3-methylbutanoyl)-4,6-di(3-methylbut-2-enyl)-6-hydroxy-cyclohexane-l,3,5-trione] by counter-current distribution and identified by spectroscopic techniques. The formation mechanism is presented and the stereochemical consequences are discussed. The anti-isohumulones are the most bitter hop compounds presently known.     

Influence of the molecular structure and the nature of the solvent on the absorption and fluorescence characteristics of rhodamines

A study of the equilibrium of the molecular forms of rhodamine 19 in aqueous and ethanolic solution is carried out by determining the absorption and fluorescence characteristics of the zwitterionic and the cationic forms of the dye. The optical properties of rhodamine 19 are compared with those obtained for rhodamine 6G and also with those previously reported for rhodamine 3B and for the molecular forms of rhodamine B in water and ethanol. Different aspects of the molecular structure of the rhodamines and solvent effects are discussed, as well as their influence on the photophysical properties of the rhodamines. The aggregation of the molecular forms of rhodamine 19 is also studied in water and ethanol.     

Phospholipid and fatty acid compositions of the lipids of the eggs and caterpillars of the silkworm,and of artificial diets and their components

The lipids of silkworm eggs in the period of diapause and embryonic and postembryonic development, of artificial feeds, and of the main lipid-containing components of artificial nutrient media have been investigated.     

Synthesis and pharmacological effects of the enantiomers of the N-phenethyl analogues of the ortho and para e- and f-oxide-bridged phenylmorphans

The N-phenethyl analogues of (1R*,4aR*,9aS*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2,3-c]pyridin-6-ol and 8-ol and (1R*,4aR*,9aR*)-2-phenethyl-1,3,4,9a-tetrahydro-2H-1,4a-propanobenzofuro[2.3-c]pyridin-6-ol and 8-ol, the ortho- (43) and para-hydroxy e- (20), and f-oxide-bridged 5-phenylmorphans (53 and 26) were prepared in racemic and enantiomerically pure forms from a common precursor, the quaternary salt 12. Optical resolutions were accomplished by salt formation with suitable enantiomerically pure chiral acids or by preparative HPLC on a chiral support. The N-phenethyl (-)- para-e enantiomer (1S,4aS,9aR-(-)-20) was found to be a mu-opioid agonist with morphine-like antinociceptive activity in a mouse assay. In contrast, the N-phenethyl (-)-ortho-f enantiomer (1R,4aR,9aR-(-)-53) had good affinity for the mu-opioid receptor (K(i) = 7 nM) and was found to be a mu-antagonist both in the [(35)S]GTP-gamma-S assay and in vivo. The molecular structures of these rigid enantiomers were energy minimized with density functional theory at the level B3LYP/6-31G* level, and then overlaid on a known potent mu-agonist. This superposition study suggests that the agonist activity of the oxide-bridged 5-phenylmorphans can be attributed to formation of a seven membered ring that is hypothesized to facilitate a proton transfer from the protonated nitrogen to a proton acceptor in the mu-opioid receptor.     

Phospholipid and fatty acid compositions of the lipids of the eggs and caterpillars of the silkworm, and of artificial diets and their components

The lipids of silkworm eggs in the period of diapause and embryonic and postembryonic development, of artificial feeds, and of the main lipid-containing components of artificial nutrient media have been investigated.Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 192–197, March–April, 1994.     

Age of the earth and the moon

We have examined the isotopic compositions of lead reported for 55 terrestrial and 65 lunar samples. The lead ages indicate that the 4.55 billion years generally accepted as the age of the solar system refers instead to the time of the breakup of the meteorite parent body.     

McBain and the centenary of the micelle

In 1913, J.W. McBain introduced the word “micelle” into surface and colloid chemistry in the context of the association of surfactant molecules in aqueous solution. This article gives a biographic account of McBain, and reviews the early work on micellar aggregation, leading up to the pioneering ideas of G.S. Hartley who introduced the first model of the spherical micelle that we would recognise today.     

Simulation of the cyclopropanecarbaldehyde and cyclopropylethanone photoisomerization processes and calculation of the quantum yields of the reactions

The cyclopropanecarbaldehyde → 2-butenal and cyclopropylethanone → 3-pentenone-2 photoisomerization processes were simulated. The calculated quantum yields of the products are in quantitative agreement with experimental data. The validity of the method proposed for the calculation of quantum yields of photochemical reactions was confirmed. It was found that if the condition of relative smallness of the optical transition probabilities as compared to the quantum beat frequency is met, the quantum yields can be quantitatively estimated with satisfactory accuracy directly from the transition probabilities without running the full calculation of the phototransformation kinetics. It was shown that the integral characteristics of photochemical reactions (quantum yields) are highly responsive to the conformational state of the molecules involved in the process.     

On the synthesis and polymerization of t-butyl-p-vinylperbenzoate and the grafting of its homo- and copolymers

The monomer initiator t-butyl-p-vinylperbenzoate (TBVP) was synthesized and its homo- and copolymerization with styrene, methacrylonitrile, isoprene and phenylmethacrylate was investigated. TBVP is preponderantly incorporated in all four systems; values of Q = 2.27 and e = ?0.13 characterize TBVP as a weak donor with a high monomer reactivity. Kinetic considerations show that all propagation steps in which TBVP takes part are faster or at least as fast as the self-propagation steps of the comonomers used. Rate constants and activation energies of the thermal decomposition of poly(t-butyl-p-vinylperbenzoate) and poly(t-butyl-p-vinylperbenzoate-co-styrene) were determined. The polymer initiators were used for grafting experiments with styrene, acrylonitrile, and methyl methacrylate. The data evaluated for the grafting efficiency, the success of grafting, and the degree of grafting show that these polymers of p-vinylperbenzoate are efficient initiators.     

Use of Isotope Effects To Understand the Present and Past of the Atmosphere and Climate and Track the Origin of Life

Stable isotope ratio measurements have been used as a measure of a wide variety of processes, including solar system evolution, geological formational temperatures, tracking of atmospheric gas and aerosol chemical transformation, and is the only means by which past global temperatures may be determined over long time scales. Conventionally, isotope effects derive from differences of isotopically substituted molecules in isotope vibrational energy, bond strength, velocity, gravity, and evaporation/condensation. The variations in isotope ratio, such as ¹⁸O/¹⁶O (δ¹⁸O) and ¹⁷O/¹⁶O (δ¹⁷O) are dependent upon mass differences with δ¹⁷O/δ¹⁸O=0.5, due to the relative mass differences (1 amu vs. 2 amu). Relations that do not follow this are termed mass independent and are the focus of this Minireview. In chemical reactions such as ozone formation, a δ¹⁷O/δ¹⁸O=1 is observed. Physical chemical models capture most parameters but differ in basic approach and are reviewed. The mass independent effect is observed in atmospheric species and used to track their chemistry at the modern and ancient Earth, Mars, and the early solar system (meteorites).     

Correlation of the electrochemical reversibility and resolution of the anode and cathode peaks of the electrode processes of hydroquinone and metol on graphite and platinum

Cyclic and direct voltammetry with linear potential sweep was used to study the potential difference of the anode and cathode peaks for hydroquinone and metol in the cyclic voltammograms (CVA) of their individual solutions on the main factors affecting the reversibility of the electrochemical process on electrodes of a graphite-epoxy composite (GEC), namely, the state of the surface of the indicator electrode, the pH of the buffer solution, and the mode of polarization. The surface state of the GEC electrode was affected by its passivation in air for various periods of time; the reversibility of the electrode process was judged by the difference between the anode and cathode potentials on the CVAs of hydroquinone and metol. A correlation was found between the degree of reversibility and the difference of peak potentials for similar electrode processes of hydroquinone and metol on the GEC electrode and other solid electrodes made of graphite materials and platinum.     

Effect of the nature of the solvent and the temperature on the frequency and intensity of the stretching vibration of the Ge-H bond in the IR spectra of 1-hydrogermatranes

Conclusions The Ge-H stretching vibration in the IR spectra of 1-hydrogermatranes varies under the influence of the solvent and the temperature as a result of the presence of the transannular Ge N bond. The change in the length of this bond with variation in the polarity of the solvent and the temperature of the solutions is smaller in germatranes than for the Si N bond in the isostructural silatranes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1758–1761, August, 1985.