Effects of Phytohormones and Jasmonic Acid on Glucosinolate Content in Hairy Root Cultures of Sinapis alba and Brassica rapa

Although some study have established hairy root cultures from brassicaceous plants with glucosinolates (GS) as characteristic secondary metabolite, studies are missing which compare hairy roots with the corresponding mother plants. Therefore, two different plant species—Sinapis alba and Brassica rapa subsp. rapa pygmeae teltoviensis—were transformed with the Agrobacterium rhizogenes strain A4. Aliphatic and indolyl GS were present in B. rapa, exhibiting larger quantities in leaves than in roots. Aromatic p-hydroxybenzyl GS were found particularly in the leaves of S. alba. However, the proportion of indolyl GS increased suddenly in transformed hairy roots of S. alba and B. rapa. Cultivation with the phytohormone kinetin (0.5 mg?L^?1) enhanced GS accumulation in B. rapa hairy roots, however not in S. alba, but 2,4-D (0.4 mg?L^?1) induced de-differentiation of roots in both species and reduced GS levels. GS levels especially of 1-methoxyindol-3ylmethyl GS increased in hairy roots in response to JA, but root growth was inhibited. While 2 weeks of cultivation in 100 to 200 μM JA were determined at optimum for maximum GS yield in S. alba hairy root cultures, 4 weeks of cultivation in 50 to 100 μM JA was the optimum for B. rapa.     

Correlations: Alkylsilane property — polynomial coefficients of the adjacency matrix of the molecular graph

Based on the characteristic polynomial coefficients (CPCs) of the adjacency matrix A′ of heterogeneous molecular graphs of the molecules containing a tetravalent heteroatom >Si< (>Ge<, >Sn<), etc. in the chain, a 13-constant additive scheme for the calculation of their physicochemical properties is obtained. The structural meaning of CPCs of the adjacency matrix A′ is established. By the formula obtained the formation enthalpies Δ _f H _{gas, 298K} ⁰ of SiC _n H_2n+2 alkylsilanes not studied experimentally are calculated.     

Components of the Lauraceae family—I : New lactonic compounds from Litsea japoncia

Six new compounds, named litsenolides A₁, A₂, B₁, B₂, C₁ and C₂, have been isolated from the roots of Litsea japonica (Japanese name “Hamabiward). Spectral and chemical evidence shows that these six compounds are three pairs of β-hydroxy-γ-methyl-αβ′-unsaturated-γ-lactones having a long carbon chain terminated with a methyl (C series), an allyl (A series) or a propargyl (B series) group. The two components of each pair differ only in the structure, cis or trans, at the double bond conjugated with the lactone group. The absolute stereochemistry of the compounds is also discussed.     

Study on solid–liquid phase equilibria in ionic liquid: 1. The solubility of alkali chloride (MCl) in ionic liquid EMISE

This paper reports the solubility of alkali chloride MCl (M is Li, Na and K) in IL EMISE was measured in the temperature range of 293.15 K to 343.15 K. The relationship between solubility, m and temperature T may be expressed in an empiric formula: ln(m/m⁰) = A₁ + A₂T₀/T + A₃T/T⁰, where m⁰ is 1 mol/kg, T⁰ is 1 K. The observed sequence of solubility is LiCl > NaCl > KCl. The fact implies that the less the radius of alkali ion, the greater is its solubility because little ion is easy to get into the interstices of IL EMISE.     

Water-soluble chiral monosulfonamide-cyclohexane-1,2-diamine-RhCp complex and its application in the asymmetric transfer hydrogenation (ATH) of ketones

Monosulfonamide ligands with heteroatom/heterocyclic systems were derived from trans-(1R,2R)-cyclohexane-1,2-diamine and complexed with [Ru(benzene)Cl₂]₂, [Cp^∗RhCl₂]₂ in situ and used in the ATH of aromatic ketones with aqueous sodium formate as the hydrogen source. The chiral secondary alcohols were obtained with >93% enantioselectivity and >89% yield. Reduction in water was faster than in isopropanol/KOH. Addition of surfactants showed little or no effects.     

Effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in hydrochloric acid solution

In this study, the effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in hydrochloric acid (HCl) solution was investigated by using dodecyl trimethyl ammonium chloride (DTAC), tetradecyl trimethyl ammonium chloride (TTAC), cetyl trimethyl ammonium chloride (CTAC), and octadecyl trimethyl ammonium chloride (OTAC) as corrosion inhibitors to uncover their structure–efficiency relationships. The effect of the alkyl chain of quaternary ammonium cationic surfactants on corrosion inhibition in HCl solution was studied under different conditions, such as corrosion inhibitor concentration, temperature, and acidity, and this was done using the weightlessness method. The results obtained show that these inhibitors have high corrosion inhibition effect on A₃ steel, and the corrosion inhibition efficiency is dependent on the length of the alkyl chain. At the same concentration, the longer the alkyl chain, the weaker the corrosion inhibition effect. When the temperature was 50 °C and the concentration of corrosion inhibitor was 70 mg/L, the corrosion inhibition efficiency order of the four cationic surfactants was DTAC > TTAC > CTAC > OTAC. Besides, the experimental results obtained show that the adsorption of the inhibitor on the A₃ steel surface conforms to the Langmuir type isotherm, and then the corresponding adsorption thermodynamic parameters were obtained according to these parameters. It was observed that ΔH, ΔS, and E_a increased with increase in the length of the alkyl chain. The adsorption of the inhibitor on the steel surface is an exothermic, spontaneous, entropy process.     

Adduct formation in LC-ESI-MS of nonylphenol ethoxylates: mass spectrometrical, theoretical and quantitative analytical aspects

The analysis of nonylphenol ethoxylate (A₉PEO_n) surfactants with LC-ESI-MS was investigated in a detailed study of the formation of different types of adducts. Part of the observations was explained by calculating their relative stabilities using molecular dynamics techniques.Strong differences in adduct formation behaviour were found for different oligomers.Beside the common sodium adducts, surfactant dimer adducts [2 × A₉PEO_1,2 + Na]⁺, adducts including a solvent molecule [A₉PEO_1,2 + MeOH + Na]⁺ and doubly charged adducts [A₉PEO_>11 + 2 × Na]²⁺ were found.Molecular dynamics calculations showed that the A₉PEO_n molecule wraps itself around the complexing sodium ion in a way that negative electronic charges on oxygen have optimum electrostatic interaction with this ion. van der Waals interactions between alkyl chains are of less importance for the stability of these adducts. Both [2 × A₉PEO_2,5 + Na]⁺ dimer and [A₉PEO_2,5 + Na]⁺ monomer adducts turned out to be stable from an energetic point of view with adducts of A₉PEO₅ being more stable than adducts of A₉PEO₂. Only for the monomer adduct the latter is in accordance with experimental observations.Consequences of the formation of several adducts per A₉PEO_n oligomer for the quantitative analysis of environmental samples were evaluated. In clean samples, it was found that the presence of short-chain A₉PEO_1,2 can cause an overestimation of long-chain A₉PEO_>2. In real environmental extracts, other processes like matrix effects have a stronger influence on the quantitative result, and therefore no significant influence of adduct formation processes could be observed. However, inclusion of [A₉PEO_1,2 + MeOH + Na]⁺ adduct signals does improve the detection limits of the two short-chain oligomers.Correct quantitative results are obtained when A₉PEO₁ and A₉PEO₂ are quantified separately, and longer oligomers with a molar calibration followed by correction of the average molar weight of the A₉PEO_>2 in the sample.     

New nonstoichiometric molybdate,tungstate, and vanadate catalysts with the scheelite-type structure

Phases of the formula A_1?xфxMO₄ with the scheelite-type structure are described where ф represents a vacancy at the A cation site and M is Mo⁶⁺, W⁶⁺, and/or V⁵⁺. Many different univalent, divalent, and trivalent A cations were used in this study. The phases with no defects, i.e., x = 0, were known except for those of the type A¹⁺_.5A³⁺_.5MO₄ where A¹⁺ is Ag or Tl and M is Mo⁶⁺ or W⁶⁺. Phases with x > 0 are generally new and were prepared for catalytic studies. An excellent correlation between catalytic properties and defect concentration has been observed.     

Study on ion–solvent interactions of alkali metal salts in pure methanol and its binary mixtures with ethane-1,2-diol by a conductometric technique

Electrolytic conductivities of some sodium salts (NaI, NaSCN, CH₃COONa) have been studied in 0, 25, 50 and 75 mass% ethane-1,2-diol + methyl alcohol mixtures at 293.15, 298.15 and 303.15 K. The limiting molar conductivity (Λ°), the association constant (K_A) and the distance of closest approach of ion (R) have been evaluated using the Fuoss conductance equation (1978). The association constant (K_A) decreases with temperature while it tends to decrease in the order: 0 mass% > 25 mass% > 50 mass% > 75 mass% ethane-1,2-diol + methyl alcohol mixtures. Thermodynamic parameters ΔH°, ΔG° and ΔS° along with the Walden products (Λ°η) are obtained and discussed. The results have been interpreted in terms of ion–solvent interactions and structural changes in the mixed solvents.     

Effect of different strains of Agrobacterium rhizogenes and nature of explants on Plumbago indica hairy root culture with special emphasis on root biomass and plumbagin production

The aim of the present study was to determine the effect of three strains of Agrobacterium rhizogenes (ATCC 15834, A4 and LBA 9402) and the nature of explants (leaf and stem) on hairy root induction, growth and plumbagin production in Plumbago indica. The first appearance of hairy roots, the transformation frequency, dry root biomass and plumbagin accumulation were found to be maximum in hairy roots induced in leaf explants infected with A. rhizogenes ATCC 15834 as compared with the other two bacterial strains. The hairy roots generated from stem explants infected with all three strains were not found to be productive in terms of the selected parameters. Finally, the insertion of the rolB gene of A. rhizogenes ATCC 15834 in hairy roots of P. indica derived from leaf explants was confirmed by PCR analysis.     

Structural studies of cerium tantalates

Structural data obtained from neutron diffraction studies of some cerium tantalate phases are presented, including the first report of the high temperature structure of a CeTaO₄ phase, Ce_0.85TaO_3.84 deduced from in situ data recorded at 900°C in vacuum. It was found that this material transformed from the low temperature LaTaO₄ type phase to the orthorhombic A2₁am structure reported here, with a unit cell of a=5.64062(2) Å, b=14.81609(6) Å and c=3.93482(1) Å. This data agrees well with the previously proposed structural transformations.     

1,9-Bis(N,N-dimethylaminomethyl)dipyrromethanes in the synthesis of porphyrins bearing one or two meso substituents

A synthesis of 5,15-disubstituted zinc-porphyrins has been developed that employs condensation of a 1,9-bis(N,N-dimethylaminomethyl)dipyrromethane+a dipyrromethane in refluxing ethanol containing zinc acetate followed by oxidation with DDQ. The N,N-dimethylaminomethylation of the dipyrromethane was achieved via Eschenmoser's reagent (N,N-dimethylmethyleneammonium iodide) in CH₂Cl₂ at room temperature. The synthesis is compatible with diverse substituents (e.g., alkyl, aryl, ester, acetal) and enables rapid synthesis of trans-AB-, A₂-, and A-porphyrins. The synthesis of >40 zinc porphyrins has been surveyed; 13 zinc porphyrins were isolated in yields of 5-20% without detectable scrambling.     

The study of the crystalline phosphates of kosnarite type structure containing different alkali metals

The incorporation possibilities of different alkali elements into crystalline phosphates A_1−xA′_xHf₂(PO₄)₃ (A=Li, Na, K, Rb, Cs) were studied, the formation regions of kosnarite solid solutions were determined. Na_0.5K_0.5Hf₂(PO₄)₃ crystal structure was studied by powder X-ray diffraction, and the distribution of alkali metals in kosnarite structure was found out. The phosphate crystallizes in the space group R3?c, with a=8.7295(1) Å, c=23.2023(4) Å, V=1531.24(4) Å³, Z=6; R_wp=6.15, R_p=4.43. The concentration region knowledge of the kosnarite phase existence and peculiarities of their phase formation in the A_1−xA′_xM₂(PO₄)₃ (M=Ti, Zr, Hf) systems allow us to choose phosphate matrice compositions suitable for solidification of reprocessing wastes of spent U-Pu nuclear fuels.     

Dimensional reductions from 2-D Nb4P2S21 to 1-D ANb2PS10 (A=Na, K, Rb, Cs, Tl) and to 0-D Tl5[Nb2S4Cl8]Cl using halide molten salts

We found new synthetic routes to obtain 1-D quaternary thiophosphate compounds and a 0-D molecular complex containing a Nb₂S₄ core from a 2-D ternary thiophosphate, Nb₄P₂S₂₁. When Nb₄P₂S₂₁ was reacted with alkali metal halides (ACl; A=Na, K, Rb, Cs) or TlCl at 500-700 °C, the -S-S-S- bridges in 2-D Nb₂PS₁₀-S-S₁₀PNb₂ were excised to form a 1-D chain, and cations were inserted between the chains to form ANb₂PS₁₀ (A=Na, K, Rb, Cs, Tl). We also found that thallium chloride (TlCl) is an excellent reagent for further excision, and it substitutes chloride ligands for the sulfur ligands of 2-D Nb₄P₂S₂₁ to form the molecular complex Tl₅[Nb₂S₄Cl₈]Cl. Crystal data for TlNb₂PS₁₀: monoclinic, Pn, a=6.9452(11) Å, b=7.3761(12) Å, 12.873(2) Å, β=104.472(3)°, and Z=2. Crystal data for Tl₅[Nb₂S₄Cl₈]Cl: orthorhombic, Immm, a=7.001(5) Å, b=9.509(7) Å, c=15.546(11) Å, and Z=2.     

A structural study of the perovskite series Ca1−xNaxTi1−xTaxO3

Compounds in the solid solution series Ca_1−xNa_xTi_1−xTa_xO₃ were synthesized at 1300 °C, followed by annealing at 850 °C or 800 °C with quenching and/or slow cooling to room temperature. Rietveld refinement of their powder X-ray diffraction patterns show that all compounds are single-phase ternary perovskites which adopt the space group Pbnm (a≈b≈√2a_p; c≈2a_p; Z=4) at ambient conditions. The unit cell parameters and cell volumes of the compounds increase regularly with increasing values of x. The coordination of the A-site cations changes throughout the series from eight for CaTiO₃ to nine for NaTaO₃. Compounds with 0?x ?0.4 have A-site cations in eight fold coordination, whereas the coordination of those with 0.4<x<0.9 is ambiguous. Analysis of the crystal chemistry of the compounds shows that the change in coordination at x=0.4 is related to the departure of the B-site cations from the second coordination sphere of the A-site cations, as in compounds with x>0.4 the A-^IIO distances become less than the A-B intercation distances. Contemporaneous with these coordination changes, the tilt angles of the BO₆ polyhedra decrease with increasing values of x. This solid solution series is unusual in that these structural and coordination changes occur regardless that Goldschmidt tolerance factors remain essentially constant at approximately 0.89, and observed tolerance factors, assuming eight fold coordination of the A-site cations, range only from 0.91 to 0.93 (0?x?0.8).     

Theory of titration curves: Locations of points of maximum slope on potentiometric heterovalent (“asymmetrical”) precipitation titration curves

By a wholly rigorous general treatment of the potentiometric titration curve representing the titration of B^m+ with A^n- to give the precipitate B_nA_m, where n ≠ m, it is shown on taking into account the effect of dilution that: (1) If $\text{n}\text{m}$ > 1, the inflection point must precede the equivalence point, but there is no inflection point if the initial concentration of the ion titrated is smaller than a certain value, which is determined by the values of m, n, and the solubility product of the precipitate. (2) If $\text{n}\text{m}$ < 1, the inflection point may follow the equivalence point — though not by more than a certain definite amount — or may precede it or coincide with it. In every such case there is a concentration of A^n- that will cause the equivalence point to coincide with an inflection point; this concentration depends on the values of m, n, and the solubility product of the precipitate. (3) Unless the difference between the equivalence and inflection points is negligibly small, the traditional treatment in which dilution is neglected gives seriously erroneous estimates of the location of the inflection point.     

The structures of eumitrins A1, A2 and B: The yellow pigments of the lichen,Usnea bayleyi(Stirt.)Zahlbr.

The yellow pigments named eumitrins A₁, A₂ and B were isolated from the lichen, Usnea bayleyi(Stirt.)Zahlbr. The modified bixanthone structures of these compounds were deduced mainly from their spectral data, and their absolute structures (2a, 3a and 4a) were established on the basis of X-ray crystallographic analysis of a transformed product (6) of tribromo-eumitrin B (5).     

Effect of chitosan on peroxidase activity and isoenzyme profile in hairy root cultures of Armoracia lapathifolia

Hairy root cultures of Armoracia lapathifolia established by infection with Agrobacterium rhizogenes LBA 9402 present a level and isoenzyme pattern of peroxidases (POD) comparable to nontransformed roots. Elicitation with chitosan (10, 50, and 100 mg/L) was used in order to improve POD production. Total POD activity increased about 170% after 48h of treatment with chitosan 100 mg/L. Elicitation effect on soluble and ionically cell-wall-bound POD fractions of A. lapathifolia hairy roots was analyzed. POD activity of the ionically cell-wall-bound protein fraction increased in the presence of chitosan in a dose-response manner. No effect on soluble POD fractions was observed, but the isoenzyme pattern analyzed by isoelectrofocusing showed an increase of an acidic isoenzyme (pI=3.4) after the elicitation treatment. The ionically cell-wall-bound protein fraction showed only basic isoenzymes, with an increase of an isoenzyme of pI=8.7, after the elicitation treatment.     

Synthesis and structural analysis of Bi2−ySryIr2O7, a new pyrochlore solid solution

This paper presents a study of the synthesis and structural properties of the new pyrochlore-type Bi_2−ySr_yIr₂O₇ series. Ten compositions with 0.0≤y≤0.9 were prepared by solid-state reaction with thermal treatments at 873, 1073 and 1323 K under atmospheric pressure conditions. Structural refinements from X-ray powder diffraction data by the Rietveld method show that all compounds of the Bi_2−ySr_yIr₂O₇ solid solution crystallize in a α-pyrochlore structure. The main structural difference when bismuth is substituted by strontium concerns the x position of the O1 (x, ?, ?). This substitution significantly increases the Bi/Sr-O1 distance and diminishes the Ir-O1 distance; this implies that the Ir-O1-Ir bond angle increases. With the Sr substitution, the IrO₆ local configuration goes from a flattened trigonal antiprism, y<0.5, to an elongated one, y>0.5, passing through an octahedral array, y∼0.5. The electrical consequences of these structural changes observed in this system are qualitatively explained with electronic structure calculations, this behavior agrees very well with those observed in other pyrochlore systems A₂M₂O₇ (A=rare earth cations or Tl⁺, Pb²⁺, or Bi³⁺, and M=Ru or Ir).     

Triterpene and steroidal glycosides from the genus <Emphasis Type="Italic">Melilotus</Emphasis> and their genins.

Three new triterpene oleanane glycosides, melilotosides A₁, B₁, and C₁, and non-glycosylated soyasapogenol B were isolated from Melilotus officinalis (L.) Pall. (Fabaceae) roots. The structures of the glycosides were proved using chemical transformations and spectral data. Melilotoside A₁ is soyasapogenol B 3-O-β-Dxylopyranoside; melilotoside B₁, soyasapogenol B 3-O-[β-D-galactopyranosyl-(1-2)-f-D-xylopyranoside]; melilotoside C₁, soyasapogenol B 3-O-[α-L-rhamnopyranosyl-(1-2)-β-D-galactopyranosyl(1-2)-β-Dxylopyranoside].