Metal bioaccumulation by the freshwater algaScenedesmus quadricauda

Bioaccumulation of six metals (Cu²⁺, Cu⁺, Mo⁶⁺, Mn²⁺, V⁵⁺, Ni²⁺) and their combinations by algaScenedesmus quadricauda was determined by using radio nuclide X-ray fluorescence (RXFA). The metals were added into the cultivation medium in concentrations corresponding with EC₅₀ value for each metal. The obtained results indicate that Ni²⁺, Cu²⁺ and Cu⁺ were accumulated in high amounts (20%, 17.5% and 15.19%) the Mo⁶⁺ ion (<0.2%) was accumulated in the lowest amount. For metal-metal interactions in accumulation of metal ions by algaS. quadricauda three types of answers were determined: inhibition (MoCu²⁺, Ni, Mn, V; VNi, Mn; MnNi, Cu²⁺, Cu⁺; Cu⁺Ni; Cu²⁺Ni; NiMn, V), enhancement (VCu⁺; Cu²⁺Mn;Cu⁺V, Mn; MnV; NiCu²⁺, Cu⁺) and neutral effect (VMo; Cu²⁺Mo; Cu⁺Mo; MuMo; NiMo).     

A Nonempirical Quantum-Chemical Study and Natural Bond Orbital Analysis of C6H5XCY3 Species (X = SO or SO2, Y = H or F)

The potential functions of internal rotation about the C² _sp—S bonds for C₆H₅XCY₃ species (X = SO or SO₂, Y = H or F) have been obtained at the MP2 (full)/6-31+G(d) level of ab initio theory. It is found that the spatial structures with the plane of C² _sp—S—C³ _sp bonds, which is near perpendicular to the benzene ring plane, are the energy-favourable conformations. The values of the rotational barrier about the C² _sp—S bond are equal to (kJ/mole): 21.2 (C₆H₅SOCH₃), 29.0 (C₆H₅SOCF₃), 20.4 (C₆H₅SO₂CH₃), and 28.2 (C₆H₅SO₂CF₃). On the basis of the Natural Bond Orbital (NBO) analysis results, it has been revealed that the double S=O bond is a strongly polarized covalent -bond, whereas -bond electrons practically are localized on the oxygen atom. The S=O bond order for aromatic sulfoxides and sulphones is mainly caused by hyperconjugational interactions according to the LP(O) ^*(S—C_ipso) and LP(O) ^*(S—C _Y ) mechanisms. In sulphones there is also the additional mechanism of hyperconjugational interactions such as LP(O^{1 *}(S—O²) and LP(O²) ^*(S—O¹). With the replacement of one hydrogen atom on the —XCY₃ group, the charge loss of the unsubstituted benzene molecule increases: —SOCH₃ < —SO₂CH₃ < — SOCF₃ < —SO₂CF₃. The substitution of the —CH₃ group for the —CF₃ group weakly influences the charge value on the sulfur atom but effects the acceptor characteristics of the substituent to a greater extent than the variation of the sulfur atom coordination.     

Excited Π states of divinyl chalcogenides and chalcophenes

Electron transitions in divinyl chalcogenides (CH₂=CHXCH=CH₂, where X is S, Se, or Te) have been analyzed using UV absorption spectra of dialkyl and alkyl vinyl chalcogenides. The following relations for the orbital energies are found: ^* < ^* < ^* < ^* for Te and ^* < ^* < ^* < ^* for S and Se. For chalcophenes, a correlation between the energy of the excited state (E ^*) of specific symmetry, the ionization potential (I) and the electron affinity (EA) is obtained:E ^*=const+(I+EA)/2. The electron affinity of divinyl chalcogenides is estimated. The correlation between the excited ^* states of divinyl chalcogenides and chalcophenes is discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 831–835, May, 1994.     

The scaled-particle theory and solvent isotope effects on the thermodynamic properties of inert solutes in water and methanol

The scaled-particle theory has been applied to the calculation of the thermodynamic changes associated with the formation of a cavity in several isotopic varieties of liquid water and methanol. From these results, the thermodynamic functions for the transfer of a cavity (or a hard-sphere solute) have been computed for the following solvent pairs: H₂OD₂O, H₂OH₂ ¹⁸O, H₂ ¹⁸OD₂ ¹⁸O, D₂OD₂ ¹⁸O, CH₃OHCH₃OD. For the last two of these solvents, density measurements required for the calculations were carried out as a function of temperature. The calculated deuterium solvent isotope effect on the heats and entropies of hard-sphere solutes in water is much greater than the¹⁸O isotope effect; the former also exhibits a more pronounced temperature dependence. The transfer functions computed for hard-sphere solutes are compared to experimental data on the transfer of various solutes from H₂O to D₂O and from CH₃OH to CH₃OD. In most of the cases examined, the cavity effect accounts for a large part of the transfer quantities measured for rare gases, hydrocarbons, and solutes containing a significant hydrocarbon substituent.     

Thermal decomposition of hydroxylammonium neodymium sulfate dihydrate

The thermal decomposition of hydroxylammonium neodymium sulfate dihydrate has been investigated by simultaneous thermogravimetry and differential thermal analysis. Chemical analysis, X-ray powder spectra and infrared spectroscopy have been employed to characterize the intermediates and the final product. The thermal decomposition can be described by the sequence (NH₃OH)Nd(SO₄)₂·2H₂O(NH₃OH)Nd(SO₄)₂ NH₄Nd₃(SO₄)₅Nd₂(SO₄)3. The first and the second reactions overlap, but the last one is well separated from the first two.     

A study of the1H NMR spectra of octaacetates of disaccharides

Summary 1. The¹H NMR spectra of octaacetates of disaccharides with different positions (11, 12, 13, 14, and 16) and configurations of the glycosidc bonds have been studied.2. The possibility has been shown of determining the position and configuration of the glycosidic bonds from¹H NMR spectra of disaccharide octaacetates.Institute of Biologically Active Substances, Far-Eastern Scientific Center, Academy of Sciences of the USSR. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 425–430, July–August, 1972.     

Spin crossover studies in tris(N,N′-dialkyldithiocarbamato)iron(III) complexes

A series of fifteen complexes of the type [Fe(RRNCS₂)₃] with symmetric (R=R=n- C₆H₁₃, n-C₈H₁₇, CH₂–CH=;CH₂, C₆H₅, C₆H₁₁ and C₆H₅CH₂), unsymmetric (R = CH₃; R = n-C₄H₉, C₆H₁₁, C₆H₅ and R = C₂H₅; R = n-C₄H₉, C₆H₁₁, C₆H₅ and i-C₃H₇) and ring substituents (RNR=pyrrolidyl and piperidyl) have been synthesized and their magnetic moments and Mössbauer spectra recorded from room temperature (RT) to liquid nitrogen temperature (LNT). Room temperature Mössbauer spectra of all the complexes exhibit an asymmetric doublet, which could be resolved into two doublets, each corresponding to low and high spin states in equilibrium. The crystal structure of tris(N, N-diallyldithiocarbamato)iron(III) shows it to be monoclinic with trigonally distorted octahedral geometry and space group C2/c. Fe–S stretching vibrations in the far i.r. region also show equilibria, HS LS. Depending on the nature of the alkyl group substituent, variable temperature magnetic moment and Mössbauer spectral studies, all the complexes may be divided into three groups; high spin complexes exhibiting spin-crossover (⁶A_1g ²T_2g), high spin complexes exhibiting spin transition (⁶A_1g ⁴T_1g) and intermediate spin complexes showing spin transition (⁴A_1g ²T_2g). On the basis of areas of the two doublets corresponding to high and low spin states, their percent contributions were calculated. Furthermore, magnetic moments of the equilibrium mixture calculated on the basis of respective areas compare well with the experimentally determined _eff values. E_Q values for both high and low spin states show linear decrease with increasing temperature.     

Theoretical and Empirical Relationships Between the Redox Potentials and <Superscript>1</Superscript>(<Emphasis Type="Italic">δ</Emphasis>→<Emphasis Type="Italic">δ</Emphasis>*) Transition Energies of Quadruply Bonded Complexes

An analysis of the available electrochemical and electronic-sectroscopic data for quadruply metal–metal bonded complexes reveals that the ¹(*) transition energy is an approximately linear function of the difference between the electrode potentials at which they are reduced and oxidized to the bond-order 3. 5 complexes. A theoretical framework for interpreting this correlation is provided by extending to the redox potentials a simple zero-differential-overlap model previously applied to ¹(*) transition energies. It is suggested on the basis of this model that the simplicity of the empirical relationship between ¹(*) energies and redox potentials is a consequence of the particular one- and two-electron energy terms that characterize these complexes; a linear relationship is not required by theory.     

MO LCAO calculations and the electronic spectra of the anions of cyclopent-4-ene-1,3-diones and indane-1,3-diones

The Hückel approximation in MO LCAO is used to show that the anion system of cyclopent-4-ene-1,3-dione should have two ^* transitions: a weak one at long wavelengths, NV₁, and a strong one at short wavelengths, C=C(1,3)V₁. An ethylene, phenyl, or acyl group at position 2 gives rise to a new strong band, NC=C(2), Nbenz, or NC=O (2). A p-nitrophenyl group at position 2 gives rise to a strong NNO₂ band, which overlaps the weak NV₁ band, while the Nbenz band becomes weak and is virtually lost from the spectrum.     

Kinetics and mechanism of the decomposition of CS2, OCS,and SCl2 in a radiofrequency pulse discharge

The identification of transient species in r.f. discharges and measurement of rate coefficients for their reactions contributes to the understanding of the complex mechanisms in r.f. plasma chemistry. Using kinetic spectroscopy in conjunction with a short-duration r.f. pulse to investigate the decomposition of CS₂, OCS, and SCl₂ at low pressure, it has been shown that the predominant primary dissociation steps are CS₂CS+S, OCSCO+S(¹D), and SCl₂S+Cl+Cl. With OCS the most important subsequent steps involved the formation and removal of S₂: S(¹D)+OCSCO+S₂(a¹), S₂(a¹)+MS₂(X³)+M, (13), and 2S₂+MS₄+M(15). Taking the previously published value of k₁₂, computer simulation gave the rate coefficient values k₁₃=6.4±2.4×10⁸ mol^–1 dm³ s^–1 and k₁₅=1.8±0.5×10¹³ mol^–2 dm⁶ s^–1 at 295±3 K.     

Thermal Decomposition of Xenon Tetroxide at 490–780 K

The decomposition of XeO₄ was studied over the temperature range 490–780 K. A reaction mechanism was proposed. A conclusion on the high vibrational excitation of O₂ molecules formed in the elementary reaction O + XeO₄ O₂ + XeO₃ and the branched-chain character of the decomposition with branching in the reaction O + XeO₃ 2O + O₂ + Xe was drawn.     

PMR spectra of 2-substituted pyrazines and the corresponding pyrazine N-oxides and N,N′-dioxides

The PMR spectra of pyrazine, its 2-substituted derivatives, and the corresponding N-oxides and N,N-dioxides were investigated. The character of the change in the chemical shifts in the N-oxides and N,N-dioxides of unsubstituted pyrazine indicates the electron-donor effect of the NO group. An additive effect of the NO groups on the chemical shifts of the ring protons is observed in pyrazine N,N-dioxide. An appreciable interaction of the substituent with the N₍₁₎O group and a weak interaction with the N₍₄₎O group occur in N-oxides and N,N-dioxides of 2-substituted pyrazines. A significant increase in the ortho and meta spin-spin coupling constants of the ring protons is noted when the nitrogen atoms are oxidized. The sign of the spin-spin coupling constant (J₃₅) through the NO group was determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 266–273, February, 1972.     

Ru(II) Chloro-Bis(bipyridyl) Complexes with Substituted Pyridine Ligands: Interpretation of Their Electronic Absorption Spectra

A number of complexes were synthesized with the general formula cis-[Ru(Bipy)₂(L)(Cl)](BF₄), where Bipy is 2,2"-bipyridine, L is pyridyne (Py), 4-aminopyridine (4-NH₂py), 4-picoline (4-Mepy), nicotin-amide (3-CONH₂py), isonicotinamide (4-CONH₂py), 3- and 4-cyanopyridine (3-CNpy, 4-CNpy), 4,4"-bipyridine (4,4"-Bipy), trans-1,2-bis(4-pyridyl)ethylene (Bpe), 4,4"-azopyridine (Azpy), pyrazine (Pyz), imidazole (Imid), and NH₃. The semiempirical CINDO-CI method was used to calculate the energies and intensities of transitions in the electronic absorption spectra. The differences observed in the spectra of these compounds are mainly due to the positions of the charge-transfer transitions d (Ru) *(L). Depending on the positions of these transitions, ligands L can be divided into three groups: 1) transitions Ru L lie in the region of the first long-wavelength band d (Ru) *(Bipy) (L = Azpy, Pyz); 2) transitions Ru L lie between the first and second bands due to the charge transfer to Bipy (L = 3-CONH₂py, 4-CONH₂py, 4,4"-Bipy, Bpe, 4-CNpy), and 3) transitions Ru L lie in the region of the second band d (Ru) *(Bipy) (L = Py, 4-Mepy, 3-CNPy, 4-NH₂py, Imid).     

Error of Atomic Charges Derived from Electrostatic Potential

The purpose of this article is to show that CHELP, CHELPG, and Merz and Kollman undergo error for the charge on atoms of HCOO^– (H₂O) _n for n = 1 6. We also demonstrate that the CHELP, CHELPG, and Merz and Kollman show error for the tendency toward change in the charges on carbons for CH₃NH⁺ ₃ (CH₃)₂NH⁺ ₂ (CH₃)₃NH⁺ (CH₃)₄N⁺.     

Polysaccharides of Saponin-Bearing Plants. XV. Structure of Glucoarabinogalactan from Acantophyllum Borszczowii Roots

The structure of the branched polysaccharide glucoarabinogalactan was investigated by periodate oxidation, methylation, and ¹³C NMR spectroscopy. The main chain consists of -16-bonded galactopyranoses. 12-Bonded D-glucopyranoses and 13-bonded D-galactopyranoses are located on the unreducing ends. There is a short side chain with -13-bonded L-arabinopyranoses.     

Triterpene glycosides from Pulsatilla chinensis

Four triterpene glycosides were isolated from the roots of Pulsatilla chinensis (Bunge) Regel (Ranunculaceae). Two new glycosides, chinensiosides A (1a) and B (2), were identified as 3-O-[-L-rhamnopyranosyl-(12)--L-arabinopyranosyl]-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid and 3-O-{-L-rhamnopyranosyl-(12)-[-D-glucopyranosyl-(14)]--L-arabinopyranosyl}-28-O-[-L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranosyl]-3,23-dihydroxylup-20(29)-en-28-oic acid. The other two glycosides were identified as previously known hederasaponin C (3) from Hedera helix and glycoside III (4) from Pulsatilla cernua.     

Kinetic Parameters for Direct Atomic Substitution Reactions

Experimental data (the rate constants and activation energies) for seven reactions of direct substitution of one atom for another D + CH₃R CH₂DR + H, D + NH₃ DNH₂ + H, D + H₂O HOD + H, F + CH₃X CH₃F + X (X = F, Cl, Br, and I) involving atoms D and F and molecules C₂H₆, H₂O, NH₃, CH₃F, CH₃Cl, CH₃Br, and CH₃I are analyzed using the parabolic model of a bimolecular radical reaction. The activation energies for the thermally neutral analogs of these substitution reactions are calculated. Atomic substitution involving deuterium atoms has a lower activation energy of a thermally neutral reaction than radical abstraction or substitution.     

Modeling water exchange on monomeric and dimeric Mn centers

Water exchange on Mn centers in proteins has been modeled with density functional theory using the B3LYP functional. The reaction barrier for dissociative water exchange on [Mn^IV(H₂O)₂(OH)₄] is only 9.6 kcal mol^–1, corresponding to a rate of 6×10⁵ s^–1. It has also been investigated how modifications of the model complex change the exchange rate. Three cases of water exchange on Mn dimers have been modeled. The reaction barrier for dissociative exchange of a terminal water ligand on [(H₂O)₂(OH)₂Mn^IV(-O)₂Mn^IV(H₂O)₂(OH)₂] is 8.6 kcal mol^–1, while the bridging oxo group exchange with a ring-opening mechanism has a barrier of 19.2 kcal mol^–1. These results are intended for interpretations of measurements of water exchange for the oxygen evolving complex of photosystem II. Finally, a tautomerization mechanism for exchange of a terminal oxyl radical has been modeled for the synthetic O₂ catalyst [(terpy)(H₂O)Mn^IV(-O)₂Mn^IV(O)(terpy)]³⁺ (terpy=2,2:6,2-terpyridine). The calculated reaction barrier is 14.7 kcal mol^–1.Contribution to the Björn Roos Honorary Issue     

Development of a procedure for the sequential extraction of substances binding trace elements in plant biomass

This work investigates how the amounts of some important substances in a plant, and their behaviour inside the plant, depend on the levels of stress placed on the plant. To this end, model plant spinach (Spinacia oleracea L.) was cultivated on soil treated with sewage sludge. The sewage sludge contained various trace elements (As, Cd, Cu, Zn), and the uptake of these trace elements placed the plant under stress. Following this, a sequential extraction procedure was employed to determine the levels and distributions of trace elements within the most important groups of compounds present in the spinach plants. Since the usual five-step sequential extraction procedure provides only general information on the distributions of elements within individual groups of organic compounds, due to the wide range of organic compounds within the individual fractions, this scheme was extended and improved through the addition of two solvent extraction steps—a butanol step (between the ethyl acetate and methanol solvent steps) and an H₂O step (after the methanol+H₂O solvent step). The distributions and levels of the trace elements within the main groups of compounds in spinach biomass was investigated using this new seven step sequential extraction (water free solvents: petroleum ether (A) ethyl acetate (B) butanol (C) methanol (D) water solvents: methanol+H₂O (1+1; v/v) (E) H₂O (F) methanol+H₂O+HCl (49.3+49.3+1.4; v/v/v) (G)). The isolated fractions were characterized using IR spectroscopy and the trace element contents were determined in the individual fractions. Lipophilic compounds with low contents of Cd, Cu and Zn were separated in the first two fractions (A, B). Compounds with higher As contents (11.5–12.8% of total content) were also extracted in the second fraction, B. These two fractions formed the smallest portion of the isolated fractions. Low molecular compounds from secondary metabolism and polar lipids were separated in the third (C) and fourth (D) fractions, and high molecular compounds (mainly polypeptides and proteins) separated in the fifth and sixth fractions (E, F). The addition of the H₂O solvent step was particularly useful for separating compounds that have a significant impact on trace element bounds. The methanol fraction was dominant for all treatments, and a significant decrease in the spinach biomass separated in this fraction was observed when the soil was treated with sewage sludge. Most of the As (35.5–38.8% of total content), Cu (45.0–51.6%) and Zn (39.8–47.2%) was also determined in this fraction. The G fraction (obtained after acid hydrolysis) contained polar compounds. Most of the Cd was also found in this fraction, as was a significant amount of Zn. Non-extractable residues formed the last fraction (polysaccharides, proteins).     

Decomposition of Nitrogen Oxides on Palladium and Angle-Resolved Measurements of Desorbing Products

Recent angle-resolved measurements of desorbing products were reviewed for decomposition of nitrogen oxides on noble metals. Two pathways for the removal of adsorbed nitrogen atoms, i.e., N(a) + NO(a) N₂O(a) N₂(g) + O(a) and 2N(a) N₂(g), were examined typically on Pd(110). The former takes place in the presence of gaseous CO and shows two-directional N₂ desorption collimated far from the surface normal in the normally directed plane along the [001] direction. The latter does not contribute in CO + NO reaction on Pd(110). The model proposed for the inclined desorption was also explained.