Dediazoniation of Arenediazonium Ions. Part XIX. Effect of thiocyanate ion in the reactions of 2,4,6-trimethylbenzenediazonium tetrafluoroborate in 2,2,2-trifluoroethanol

The dediazoniation of 2,4,6-trimethylbenzenediazonium tetrafluoroborate ( 1 ) in 2,2,2-trifluoroethanol (TFE) was studied in the presence of potassium thiocyanate. The effect of added salt on the dediazoniation rate, the N_α-N_β rearrangement (Eqn. 2), the exchange of the ¹⁵N-labelled diazo group with molecular nitrogen (Eqn. 3), and the reaction products was determined. With 0.3_M KSCN a dediazoniation-rate increase of 16.5% was achieved, and the amounts of rearranged and exchanged product were reduced to 88% and 70%, respectively, of the values found in pure TFE. The dediazoniation products formed are ArF ( 3 ), ArOCH₂CF₃ ( 4 ), ArSCN ( 5 ), ArNCS ( 6 ) and traces of 5, 7-dimethylindazole ( 7 ). All the data are in agreement with, and support the previously proposed mechanism (Equ. 1) of heterolytic dediazoniation of arenediazonium salts.     

Moving reaction boundary and isoelectric focusing: IV. Systemic study on Hjertén's pH gradient mobilization

In this paper, Hjertén's mobilization of pH gradient in IEF was systemically and quantitatively analyzed with the R_r value of judgment expression comparing the fluxes of hydrogen and hydroxyl ions. The theoretical results show that (i) there is R_r = 0, viz., quasi‐equal fluxes of proton and hydroxyl ion, in a classic IEF with sulfuric acid and sodium hydroxide used as the anolyte and catholyte, respectively, this is the main reason why pH gradient is quite stable in IEF; (ii) but if the salt of sodium sulfate is added into the sodium hydroxide, there is R_r > 0, viz., the flux of proton being higher than that of hydroxyl ion, the R_r value implies a cathodic mobilization of pH gradient, and the higher the R_r value is the faster the cathodic mobilization becomes; (iii) if the salt is added into the sulfuric acid, there is R_r < 0, the R_r value indicates an anodic mobilization, and the smaller the R_r value is the faster the anodic mobilization turns. To test these theoretical results above, a novel procedure was developed for the run of classic IEF followed by Hjertén's mobilization of pH gradient. The strict experiments were in well coincidence with the theoretical results. The results have obvious significances for the mechanism and development of Hjertén's mobilization.     

Dediazoniation of arenediazonium ions in homogeneous solution. Part VIII. Reaction kinetics and products in dimethyl sulfoxide

p-Nitrobenzenediazonium tetrafluoroborate dissolved in dimethylsulfoxide (DMSO) at 50° forms p-nitrophenol in 88–90% yield. The phenolic oxygen atom originates exclusively from the oxygen atom of DMSO as demonstrated by the use of ¹⁸O-labelled DMSO. The first-order rate of dediazoniation is the same under N₂ as it is in the presence of air. The rate is little influenced by the addition of benzene or iodobenzene. However, the products formed in the presence of these additives are significantly different. UV. spectra and the reactivity of diazonium salt solutions in DMSO when mixed with reagents in aqueous solution demonstrate that a relatively stable charge-transfer complex is formed between the diazonium ion and DMSO. The product analyses and the kinetic and spectral results of dediazoniation in DMSO with and without additives are consistent with a mechanism in which the rate-limiting step is the formation of a p-nitrophenyl radical from the charge-transfer complex. p-Nitrophenol and the products with benzene and iodobenzene are formed in subsequent fast competition steps. In the presence of small amounts of pyridine the dediazoniation is much faster and follows a different kinetic law. Pyridine effectively competes with DMSO in the reaction with diazonium ions.     

Determination of avoparcin in animal tissues and milk using LC‐ESI‐MS/MS and tandem‐SPE

A highly sensitive and selective method using LC‐ESI‐MS/MS and tandem‐SPE was developed to detect trace amounts of avoparcin (AV) antibiotics in animal tissues and milk. Data acquisition using MS/MS was achieved by applying multiple reaction monitoring of the product ions of [M + 3H]³⁺ and the major product ions of AV‐α and ‐β at m/z 637 → 86/113/130 and m/z 649 → 86/113/130 in ESI(+) mode. The calculated instrumental LODs were 3 ng/mL. The sample preparation was described that the extraction using 5% TFA and the tandem‐SPE with an ion‐exchange (SAX) and InertSep C18‐A cartridge clean‐up enable us to determine AV in samples. Ion suppression was decreased by concentration rates of each sample solution. These SPE concentration levels could be used to detect quantities of 5 ppb (milk), 10 ppb (beef), and 25 ppb (chicken muscle and liver). The matrix matching calibration graphs obtained for both AV‐α (r >0.996) and ‐β (r >0.998) from animal tissues and milk were linear over the calibration ranges. AV recovery from samples was higher than 73.3% and the RSD was less than 12.0% (n = 5).     

Dediazoniation of 1-naphthalenediazonium tetrafluoroborate in aqueous acid and in micellar solutions

We have measured the rates and product yields of dediazoniation of 1-naphthalenediazonium (1ND) tetrafluoroborate in the presence and absence of sodium dodecyl sulfate (SDS) micellar aggregates by employing a combination of UV–vis spectroscopy and high-performance liquid chromatography (HPLC) measurements. Kinetic data were obtained by a derivatization procedure with product yields were determined by HPLC. HPLC chromatograms show that in aqueous acid and in micellar solutions only one dediazoniation product is formed in significant quantities, 1-naphthol (NOH), and the observed rate constants (k_obs) are the same when 1ND loss is monitored spectrometrically and when NOH formation is monitored by HPLC. Activation parameters were obtained both in the presence and absence of SDS micellar aggregates. In both the systems, the enthalpies of activation are high and the entropies of activation are positive. The enthalpy of activation in the absence of SDS is very similar to that in the presence of SDS micelles, but the entropy of activation is lower by a factor of 4. As a consequence, SDS micelles speed up the thermal decomposition of 1ND and increase k_obs by a factor of 1.5 when [SDS] = 0.02 M. In contrast, results obtained in the presence of complexing systems such as crown ethers and polyethers show significant stabilization of the parent arenediazonium ions. Kinetic and HPLC data are consistent with the heterolytic D_N + A_N mechanism that involves the rate-determining fragmentation of the arenediazonium ion into a very reactive phenyl cation that reacts competitively with available nucleophiles. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 301–309, 2008     

Surface characteristics of polysulfoalkyl methacrylates

Coated hydroxyethyl methacrylate-sodium sulfoalkyl methacrylate copolymer films were surface characterized. The contact angle hysteresis increases and the receding angle decreases with increasing alkyl side-chain length, while the advancing angle decreases with hydration time. It was found that the buoyancy slopes of the advancing (r_a) and receding (r_r) process determined by the Wilhelmy plate method were not parallel. The ratio of r_a to r_r was greater than 1, and increases with the alkyl side-chain length and the hydration time, contrary to that of polyhydroxyethyl methacrylate, where r_a/r_r was less than 1. The slope ratio would be suppressed in solution with added salt, revealing that the reorientation and expansion of the polymer chain in water is being suppressed. X-ray photoelectron spectroscopy (XPS) analysis of the surface of these copolymers showed a striking enrichment of the sulfonate groups in the surface. The zeta potential was between −40 and −50 mV as measured by the streaming potential method. During dehydration, along with a decrease in sulfur and sodium concentration in the surface, the carbon 1s peak at the high binding energy decreased and the alkyl carbon main peak increased. The surface tension of aqueous solutions of sulfoalkyl methacrylate monomers and homopolymers decreases with increasing alkyl side-chain length, which may contribute to the decrease in water-polymer film interfacial tension and thus the increase in the slope ratio.     

Stereoselective Synthesis of γ-(Acyloxy)carboxylic Acids and γ-Lactones Featuring the Switch of Stereopreference of Candida antarctica Lipase B in Sodium γ-Hydroxycarboxylate Homologues

Scalable protocols of straightforward synthesis of enantiomeric γ-(acyloxy)carboxylic acids and γ-lactones are presented. The key step is lipase-catalyzed stereoselective acylation of γ-hydroxycarboxylic acid sodium salt in organic solvent followed by acidification of the product, extraction and acidic relactonization of the unreacted enantiomer. The mixture of γ-(acyloxy)carboxylic acid and γ-lactone is separated either by extraction with solution of sodium bicarbonate or by distillation. A switch of enantioinduction of Candida antarctica lipase B along homologous nucleophiles from R configuration of γ-hydroxyhexanoic acid salt to S configuration of the C7 and longer-chain homologues has been disclosed. Both enantiomers of γ-(acyloxy)pentanoic acids; γ-(acetyloxy)octanoic and -nonanoic acids with S configuration; [(1S,5R)-5-(chloroacetyloxy)cyclopent-2-en-1-yl]acetic acid and enantiomeric γ-lactones derived from them were prepared with e. r. >98.5/1.5. The rates of acylation of C5 to C9 homologous salts differ by three orders of magnitude but remain applicable for preparative synthesis by variation of the enzyme loading and reaction time.     

Determination and Validation of an LC Method for Fluvoxamine in Tablets

A new, simple, rapid and specific reversed-phase high-performance liquid chromatography (HPLC) method was developed and validated for the determination of fluvoxamine in pharmaceutical dosage forms. The HPLC separation was achieved on a C₁₈ μ-Bondapack column (250 mm × 4.6 mm) using a mobile phase of acetonitrile–water (80:20, v/v) at a flow rate of 1 mL min⁻¹. Proposed method is based on the derivatization of fluvoxamine with 1,2-naphthoquinone-4-sulphonic acid sodium salt (NQS) in borate buffer of pH 8.5 to yield a orange product. The HPLC method is based on measurement of the derivatized product using UV-visible absorbance detection at 450 nm. The method was validated for specificity, linearity, precision, accuracy, robustness. The degree of linearity of the calibration curves, the percent recoveries of fluvoxamine, the limit of detection and quantification, for the HPLC method were determined. The assay was linear over the concentration range of 45–145 ng mL⁻¹ (r = 0.9999). Limit of detection and quantification for fluvoxamine were 15 and 50 ng mL⁻¹, respectively. The results of the developed procedure (proposed method) for fluvoxamine content in tablets were compared with those by the official method. The method was found to be simple, specific, precise, accurate, reproducible and robust.     

The pressure effect study on the burning rate of ammonium nitrate-HTPB-based propellant with the influence catalysts

The burning rate of AN–HTPB-based propellant catalysed with chromium salt has been studied using conventional strand burner under the various pressure range, i.e. from atmospheric pressure to 6.897 MPa and verified with Piobert law, i.e. r = aP ⁿ . At atmospheric pressure, the burning rate AN–HTPB propellant was being accelerated with the chromium-based catalysts used. In case of lead chromate-catalysed system, burning rate was observed 2.655 times higher than burning rate (r = 0.200 mm s⁻¹) of virgin AN–HTPB propellant sample. However, the Copper chromate-catalysed propellant burned with slower rate (r = 0.160 mm s⁻¹) than the virgin AN–HTPB propellant sample. The burning rate of all catalysed propellant samples are found to be the pressure sensitive and accelerated higher with rise of pressure. The highest burning rate (r = 2.422 mm s⁻¹) was recorded with ammonium dichromate and lowest (r = 1.40 mm s⁻¹) with lead chromate-catalysed propellant sample with the rise of pressure up to 6.897 MPa at different pressures. A linear relationship was observed between the burning rate and pressure rise which followed the Piobert law, i.e. r = aP ⁿ . The pressure index (n) values of AN–HTPB-based samples were calculated higher when catalysed with ammonium dichromate, Copper Chromate, Cr₂O₃, Potassium dichromate (n = 0.525, 0.555, 0.429, and 0.408 respectively) and lower (n = 0.226) with lead chromate compared to virgin sample (n = 0.405). Higher value indicates the positive effect on accelerating the burning rate with catalyst at higher pressure ranges.     

Dediazoniations of Arenediazonium Ions. Part XXI. Dediazoniation of Arenediazonium Ions Complexed with Crown Ethers

The evaluation of the dediazoniation kinetics of various m- and p-substituted benzenediazonium tetrafluoroborates in 1,2-dichloroethane at 50° in the presence of 18-crown-6, 21-crown-7 and dicyclohexano-24-crown-8 demonstrates that the rate constant for the dediazoniation within the complex (k₂) is smallest, and the equilibrium constant for complex formation (K) is largest for the complexes with 21-crown-7 (cf. Scheme 1). The logarithms of the equilibrium constants (K) for complex formation with each of the crown ethers studied correlate well with Hammett's substituent constants, σ, to give reaction constants ρ = 1.18–1.38. A linear correlation between the logarithms of the rate constants for the dediazoniation within the complex with those of the dediazoniation rate constants of uncomplexed diazonium ions (log k₂ vs. log.k₁), found for most substituted diazonium salts, indicates that the dediazoniation mechanism of the complexed diazonium ions is not significantly different from that of the free ions. For very electrophilic diazonium ions (p-Cl, m-CN), k₂ was much larger than expected on the basis of the linear log k₂ vs. log k₁ relationship. Analysis of the dediazoniation products showed that this was due to a change in mechanism from heterolytic to homolytic dediazoniation. The complexation rate of diazonium salts by crown ethers (k_c) is practically diffusion controlled and does not change much with the size of the crown ether. The decomplexation rate (k_d), however, is significantly lower for complexes with 21-crown-7, than for those with 18-crown-6 and dicyclohexano-24-crown-8, and is therefore the reason for the variations in the equilibrium constant (K) and thus for the fact that complexes of arenediazonium salts with 21-crown-7 are the most stable. The amounts of the N_α-N_β rearrangement, as well as those of the exchange of the ¹⁵N-labelled diazonio group with external nitrogen during dediazoniation of p-toluenediazonium salt were independent of the addition of crown ethers. A dediazoniation mechanism involving a charge transfer, as well as an insertion-type diazonium ion-crown ether complex is proposed. In this mechanism, dediazoniation of the insertion complex does not take place directly, but through the charge-transfer complex.     

Studies of the polymerization of diallyl compounds. XXVII. Copolymerization of diallyl tartrate with several vinyl monomers

The radical copolymerization of diallyl tartrate (DATa) (M₁) with diallyl succinate (DASu), diallyl phthalate (DAP), allyl benzoate (ABz), vinyl acetate (VAc), or styrene (St) was investigated in order to disclose in more detail the characteristic hydroxyl group's effect observed in the homopolymerization of DATa. In the copolymerization with DASu or DAP as a typical diallyldicarboxylate, the dependence of the rate of copolymerization on monomer composition was different for different copolymerization systems and unusual values larger than unity for the product of monomer reactivity ratios, r₁r₂, were obtained. In the copolymerization with ABz or VAc (M₂), the r₁ and r₂ values were estimated to be 1.50 and 0.64 for the DATa/ABz system and 0.76 and 2.34 for the DATa/VAc system, respectively; the product r₁r₂ for the latter copolymerization system was found again to be larger than unity. In the copolymerization with St, the largest effect due to DATa monomer of high polarity was observed. Solvent effects were tentatively examined to improve the copolymerizability of DATa. These results are discussed in terms of hydrogen-bonding ability of DATa.     

Effects of metal salts on polymerization. Part III. Radical polymerizabilities and infrared spectra of vinylpyridines complexed with zinc and cadmium salts

Radical polymerization of 4-vinylpyridine (4-VP), 2-vinylpyridine (2-VP), and 2-methyl-5-vinylpyridine (MVP) was studied in concentrated DMF solutions of ZnCl₂, ZnBr₂, ZnI₂, Zn(CH₃COO)₂, and Cd(CH₂COO)₂ at 50°C. Polymerization of 4-VP and MVP was accelerated by the addition of the metal salts, while the polymerization of 2-VP was greatly retarded. The sequence of the accelerating effect of metal salts for 4-VP was in the following order: Cd(CH₃COO)₂ > ZnCl₂ > Zn(CH₃COO)₂ > ZnBr₂ > ZnI₂. This sequence is almost the same as that reported in a previous report for MVP. However, the order was reversed for the retarding effect on the polymerization of 2-VP. At the intermediate concentration of metal salts, polymerization of 4-VP proceeded heterogeneously, which was explained by considering crosslinking of poly-4-VP by the metal ion. Since a linear correlation between the rate R_p and the degree of polymerization was observed for the 4-VP–Zn(CH₃COO)₂ system, the accelerating effect was postulated to be due to the enhancement in k_p. Results of copolymerization of VP with styrene as M₂ in a concentrated solution of Zn(CH₃COO)₂ indicated the strong activation of 4-VP by complex formation (r₁ = 2.7 ± 0.5, r₂ = 0.08 ± 0.03), whereas the change in the monomer reactivity of MVP is smaller (r₁ = 2.0 ± 0.2, r₂ = 0.35 ± 0.05). The behavior of 2-VP was abnormal (r₁ = 3.35 ± 0.3, r₂ = 0.55 ± 0.15, then r₁r₂ > 1), which was attributed to the steric effect by complex formation. Solid complexes formed between pyridine, 4-VP, 2-VP, or MVP and zinc salts were prepared as samples for infrared spectroscopy. The shifts in infrared absorption bands of these amines were studied by comparing the infrared spectra of the amines before and after the complex formation, and the results were interpreted in terms of electronic as well as steric interactions of metal salts with ligands. Conjugation of the metal salt with the ligand π-orbitals was necessary to explain both infrared spectra and polymerization results.     

Chemical bond breaking/forming as a Franck–Condon electronic process

We describe chemical bond changes as Franck–Condon electronic processes within a new theoretical ansatz that we call ‘rigged’ Born–Oppenheimer (R-BO) approach. The notion of the separability of nuclear and electron states implied in the standard Born–Oppenheimer (BO) scheme is retained. However, in the present scheme the electronic wave functions do not depend upon the nuclear coordinate (R-space). The new functions are obtained from an auxiliary Hamiltonian corresponding to the electronic system (r-coordinates) submitted to a Coulomb potential generated by external sources of charges in real space (α-coordinates) instead of massive nuclear objects. A stationary arrangement characterized by the coordinates α_0A, is determined by a particular electronic wave function, ψ(r;α_0A); it is only at this stationary point, where an electronic Schrödinger equation: H_e(r,α_0A)|Ψ(r;α_0A)=E(α_0A)|Ψ(r;α_0A) must hold. This equation permits us to use modern electronic methods based upon analytic first and second derivatives to construct model electronic wave functions and stationary geometry for external sources. If the set of wave functions {Ψ(r;α_0A)} is made orthogonal, the energy functional in α-space, E(α;α_0A)=Ψ(r;α_0A)|H_e(r,α_0A)|Ψ(r;α_0A) is isomorphic to a potential energy function in R-space: E(R;α_0A)=Ψ(r;α_0A)|H_e(r,R)|Ψ(r;α_0A). This functional defines, by hypothesis, a trapping convex potential in R-space and the nuclear quantum states are determined by a particular Schrödinger equation. The total wave function for the chemical species A reads as a product of our electronic wave function with the nuclear wave function (Ξ_ik(R;α_0A)): Φ_ik(r,R)=Ψ_i(r,α_0A)Ξ_ik(R;α_0A). This approach facilitates the introduction of molecular frame without restrictions in the R-space. Two molecules (characterized with different electronic spectra) that are decomposable into the same number of particles (isomers) have the same Coulomb Hamiltonian and they are then characterized by different electronic wave functions for which no R-coordinate ‘deformation’ can possibly change its electronic structure. A bond breaking/forming process must be formally described as a spectroscopic-like electronic process. The theory provides an alternative to the adiabatic as well as the diabatic scheme for understanding molecular processes. As an illustration of the present ideas, the reaction of H₂+CO leading to formaldehyde is examined in some detail.     

A partial recurrence relation for reduced class coefficients of the symmetric group

An expression for the product of a single-cycle class [(1)^{N - P}(p)]_N and an arbitrary class [(1)^l1(2)^l …? (N)^lN]_N of the symmetric group has recently been conjectured. This expression involves a sum over a relatively small number of reduced class sums, depending on p indices. A further conjecture is formulated and demonstrated, according to which reduced class coefficients (RCCS ) involving cycles whose length is expressed by means of a single index can be related to corresponding coefficients in the product of [(1)^{N - P+1}(p - 1)]_N with an arbitrary class sum. Consequently, the problem of evaluating the general class sum product reduces to that of obtaining a relatively small set of fundamental RCCS containing no single-index cycles. The conjectures mentioned can be used to evaluate the product [(1)^{N - p}(p)]_N · [(1)^{N - q}(q)]_N in terms of fundamental RCCS that can all be obtained from the product [(r)]_r · [(r)]_r, where r = min(p, q). For the latter product, we use a result due to Boccara.     

The effect of stoichiometry on curing and properties of epoxy–clay nanocomposites

Epoxy–clay nanocomposites have been prepared with an organically modified montmorillonite. The epoxy network was based on diglycidyl ether of bisphenol A (DGEBA) cured with diaminodiphenylmethane (DDM). The stoichiometry DGEBA–DDM was varied, the molar ratio of amine hydrogen/epoxy groups, r, ranged from 0.85 to 1.15. The influence of stoichiometry on curing and properties of the nanocomposites was studied using differential scanning calorimetry, dynamic mechanical thermal analysis and X-ray diffraction. All nanocomposites had intercalated clay structures. The clays accelerated the curing reaction whose rate was also increased when increasing r. The heat of reaction, −ΔH (J/g epoxy), increased as r increased, reaching a constant value for r ≥ 1. In the presence of clays −ΔH was lower than in the neat DGEBA–DDM. The glass transition temperature (T _g) of the neat epoxy thermosets reached a maximum at r = 1; however, the nanocomposites showed the T _g maximum at 0.9 < r < 1. The presence of clay lowered the T _g for r > 0.94 and raised T _g for r ≤ 0.85. The elastic modulus of neat epoxy thermosets reached a maximum in the rubber state and a minimum in the glassy state at r = 1. The nanocomposites showed similar behavior, but the maximum and the minimum values of the elastic modulus were reached at stoichiometry r < 1. The comparison of the properties of neat epoxy with those of the nanocomposites varying the stoichiometry indicates that the clay itself induces stoichiometric changes in the system.     

LC Determination of 4-Bromoaniline in Green Algae Chlamydomonas reinhardtii After Continuous-Flow Microextraction

In this study, the determination of 4-Bromoaniline (4-BA) in green algae Chlamydomonas reinhardtii (C. reinhardtii) was investigated by applying continuous-flow microextraction (CFME) combined with high-performance liquid chromatography (HPLC). Continuous-flow microextraction was conducted in a homemade glass chamber, i.e. the sample solution flowed through a constant volume drop of solvent in the chamber at a constant flow rate. The effects of different factors on extraction efficiencies were also investigated and these factors included the kind of extraction solvent, solvent drop volume, sample flow rate, extraction time and addition amount of salt. Under the optimum extraction conditions (extraction solvent, carbon tetrachloride; solvent drop volume, 3.5 μL; sample flow rate, 1.0 mL min⁻¹; extraction time, 10 min; no addition of salt), the calibration plot was set up by plotting peak area against a series of 4-Bromoaniline concentrations (0.01–10 μg mL⁻¹) in aqueous solution. The correlation coefficient (r) was 0.9990. The limit of detection (LOD) was 0.6 ng mL⁻¹. The precision of this method was obtained by successive five time analyses of 100-ng mL⁻¹ standard solution of 4-Bromoaniline, and the relative standard deviation (RSD) was 3.5%. The concentration factor was calculated by the ratio of peak area of the analyte obtained after and before extraction and found to be 10.6. 4-Bromoaniline residues in Chlamydomonas. reinhardtii cells and tap water samples were satisfactorily analyzed according to the method described above.     

A novel ultra high‐performance liquid chromatography‐tandem mass spectrometry method for the simultaneous determination of xanthones and steroidal saponins in crude and salt‐processed Anemarrhenae Rhizoma aqueous extracts

We established a rapid and sensitive ultra high‐performance liquid chromatography tandem mass spectrometry method for the simultaneous quantification of xanthones and steroidal saponins in rat plasma. Chromatographic separation was achieved on a C₁₈ column with a mobile phase comprising acetonitrile and 0.1% formic acid. The detection was performed by negative electrospray ionization in multiple reaction monitoring mode. The validated method showed good linearity within the tested range (r > 0.9945). The intra‐ and interday precision at high, medium, and low concentrations was less than 7.96%. The bias of accuracies ranged from −1.92 to 9.62%. The extraction recoveries of the compounds ranged from 84.78 to 88.69%, and the matrix effects ranged from 96.76 to 108.59%. This method was successfully applied to a pharmacokinetic comparison of crude and salt‐processed Anemarrhenae Rhizoma aqueous extracts after oral administration in rats. The maximum plasma concentration and area under concentration–time curve of timosaponin BIII and timosaponin AIII increased significantly (P < 0.05 or 0.01) and those of timosaponin BII decreased significantly (P < 0.05) after processing. These results could contribute to the clinical application of crude and salt‐processed Anemarrhenae Rhizoma and reveal the processing mechanism.     

Conformational properties of <Emphasis Type="Italic">ortho</Emphasis>-nitrobenzenesulfonamide in gas and crystalline phases. Intra- and intermolecular hydrogen bond

A combined gas-phase electron diffraction and quantum chemical (B3LYP/6-311+G**, B3LYP/cc-pvtz, MP2/cc-pvtz) study of molecular structure of 2-nitrobenzenesulfonamide (2-NBSA) was carried out. Quantum chemical calculations showed that 2-NBSA has four conformers, two of which are stabilized by intramolecular hydrogen bond. The latter (with the S–N bond in a close to orthogonal position around the phenyl ring and differing from each other by staggered or eclipsed positions of the N–H and S=O bonds in the SO₂NH₂ group) presented in a saturated vapor over 2-NBSA at T = 433 (3) K in commensurable amounts. Experimental internuclear distances (Ǻ) for the staggered conformer are (?): r _h1(C–H)_av. = 1.071(9), r _h1(C–C)_av. = 1.390(4), r _h1(C–S) = 1.789(8), r _h1(S=O)_av. = 1.427(6), r _h1(S–N) = 1.644(6), r _h1(N–O)_av. = 1.221(4), r _h1(C′–N) = 1.487(8), r _h1(N–H)_av. = 1.014. Calculations at B3LYP/cc-pvtz level were performed to determine the structure and the energies of the transition states between conformers. It was shown that the conformer structures of free molecule differ from those of a molecule stabilized by intermolecular hydrogen bonds in a crystal. Influence of a substituent X (X = –CH₃, –NO₂) on conformational features of the ortho-substituted benzenesulfonamide was established.     

The Effect of N-alkyl Substitution on Binding of Polycarboxylic Anions by Linear Polyammonium Cations

The interaction between three N-alkyl-substituted polyamines[1,1,4,4-tetramethylethylenediamine, 1,1,4,7,7,-pentamethyldiethylenetriamine,and 1,1,4,7,10,10-hexamethyltriethylenetetramine; general formula C_3nN_nH_(7n+2)] with fourpolycarboxylic ligands (malonate, citrate, 1,2,3-propanetricarboxylate, and1,2,3,4-butanetetracarboxylate) has been studied potentiometrically in aqueous solution at25°C. For all the systems, the species ALH_r (r = 1, 2 ... n + m – 1;n and m are the maximum degrees of protonation for the amine A and the carboxylicligand L, respectively) are formed. The stability of these species is quite high(in particular, that of species with r = n and r = n + 1) and is a linear functionof the charges involved in the formation reaction. The effect of N-alkyl substitutionis quite small: comparison with the analogous unsubstituted polyamines C_(2n–2)N_nH_(5n–2) shows only a small decrease in stability. On average we have–G ^o/n = 5.9 kJ-mol^–1 for N-alkyl-substitutedamines and 6.6 kJ-mol^–1 for unsubstituted ones (ndenoting the number of possible salt bridges). Other linear charge—stabilityrelationships are considered.     

Effect of sodium cation on the electrochemical reduction of CO<Subscript>2</Subscript> at a copper electrode in methanol

The electrochemical reduction of CO₂ with a Cu electrode in methanol was investigated with sodium hydroxide supporting salt. A divided H-type cell was employed; the supporting electrolytes were 80 mmol dm⁻³ sodium hydroxide in methanol (catholyte) and 300 mmol dm⁻³ potassium hydroxide in methanol (anolyte). The main products from CO₂ were methane, ethylene, carbon monoxide, and formic acid. The maximum current efficiency for hydrocarbons (methane and ethylene) was 80.6%, at −4.0 V vs Ag/AgCl, saturated KCl. The ratio of current efficiency for methane/ethylene, r _f(CH₄)/r _f(C₂H₄), was similar to those obtained in LiOH/methanol-based electrolyte and larger relative to those in methanol using KOH, RbOH, and CsOH supporting salts. In NaOH/methanol-based electrolyte, the efficiency of hydrogen formation, a competing reaction of CO₂ reduction, was suppressed to below 4%. The electrochemical CO₂ reduction to methane may be able to proceed efficiently in a hydrophilic environment near the electrode surface provided by sodium cation.