Iron‐Mediated Cleavage of C?C Bonds in Vicinal Tricarbonyl Compounds in Water

Three of a kind : Vicinal tricarbonyl compounds undergo C? C cleavage mediated by ferric ions (see scheme). The observed cleavage of ninhydrin and dehydroascorbic acid has relevance for amino acid detection and the metabolism of vitamin C.

     

Solving an inverse problem for a generalized time-delayed Burgers-Fisher equation by Haar wavelet method

In this paper, a numerical method consists of combining Haar wavelet method and Tikhonov regularization method to determine unknown boundary condition and unknown nonlinear source term for the generalized time-delayed Burgers-Fisher equation using noisy data is presented. A stable numerical solution is determined for the problem. We also show that the rate of convergence of the method is as exponential $\Bigl(O\left(\frac{1}{2^{J+1}}\right)\Bigr)$, where $J$ is maximal level of resolution of wavelet. Some numerical results are reported to show the efficiency and robustness of the proposed approach for solving the inverse problems.     

Interaction of nicotine with π and σ electron acceptors

Interaction of nicotine with tetracyanoethylene and iodine was investigated spectrophotometrically and found to form strong CT complexes (n−π and n-σ^*, respectively). The donor site involved in CT interaction is the pyrrolidine nitrogen. The nicotine-I₂ complex exists as the ionic structure (nicotine) I⁺-I ₃ ⁻ . Formation constants of the CT complexes in various solvents were determined from 10 to 25°C and are discussed in terms of the nature of the electron acceptor and solvent polarity. Solid CT complexes were synthesized and were characterized by microchemical analysis and infrared spectra techniques.     

Mono- and Bi-nuclear metal complexes of arylidene-anthranilic acidSchiff bases

Arylidene-anthranilic acidSchiff base complexes with Th(IV), UO₂(II), La(III), Ce(III), and Zr(IV) have been isolated and studied by several techniques, e.g. elemental analysis, electronic and IR spectra and conductance measurements. It is concluded that the salicylideneanthranilic acidL ₃ is coordinated to the metal ion as bivalent tridentate ONO ligand (L ^–2) while the other ligands behave as monovalent bidentate ON ligands. Furthermore, the molecular structure effect of these compounds on their tendency towards complex formation was investigated and discussed. The possibility that the Cu(II) complex ofL ₃ can act as bidentate ligand, coordinating through itscis-oxygen atoms to form binuclear metal complexes was studied.

---

Ein- und zweikernige Metall-Komplexe von Aryliden-Anthranilsäure-Schiff-Basen

Zusammenfassung Es wurden Aryliden-Anthranilsäure-Schiff-Basen mit Th(IV), UO₂(II), La(III), Ce(III) und Zr(IV) isoliert und mittels Elementaranalysen, Elektronen-und IR-Spektroskopie und Leitfähigkeitsmessungen untersucht. Es wird aus den Untersuchungen geschlossen, daß Salicylidenanthranilsäure (L ₃) als bivalenter dreizähniger ONO-Ligand (L ^–2) an das Metallion koordiniert, währenddessen die anderen Liganden als monovalente zweizähnige Liganden agieren. Außerdem wurden Struktureffekte dieser Verbindungen in bezug auf ihre Komplexbildungstendenz untersucht. Die Möglichkeit, daß der Cu(II)-Komplex vonL ₃ über die Koordination mit dencis-Sauerstoff-Atomen und unter Bildung eines zweikernigen Metallkomplexes als zweizähniger Ligand agieren kann, wurde untersucht.

     

Development of a stability-indicating capillary electrophoresis method for norfloxacin and its inactive decarboxylated degradant

A simple, accurate, precise, rapid and sensitive stability-indicating capillary electrophoresis (CE) method was optimized and validated for the simultaneous determination of norfloxacin and its inactive decarboxylated degradant in pharmaceuticals. The univariant method was used to optimize electrophoretic factors including injection time, separation voltage and column temperature. Electrolyte concentration and pH were optimized using the factorial design and response surface methods. The optimum conditions obtained were: 10 mmol l^− 1 phosphate at pH 2.5, hydrodynamic injection time of 8 s at pressure 0.5 p.s.i., separation voltage 25 kV and column temperature 25 °C. The separation was carried out into a fused-silica capillary column (31.2 cm length × 50 μm i.d.) with detection at 301 and 285 nm for the intact drug and the degradant, respectively using a diode array detector. For both analytes, the method enjoys wide dynamic range (1-50 μg ml^− 1) with good detectability (limits of detection 0.11 μg ml^− 1). In addition, acceptable accuracy (recovery > 95%); and good repeatability and intermediate precision (RSD < 3.5%) were obtained.     

Specific heat and phase transition of (Li1−xKx)2SO4 single crystals

A specific heat study of (Li_1–xK_x)₂SO₄ — LKS — mixed crystals has been made in a wide concentration rangex covering the temperature range 300–800 K. The phase diagram was determined. It is shown that a variation of the Li⁺:K⁺ concentration changes the critical behaviour of the specific heat. The results are discussed in terms of scattering mechanisms of energy carriers.

---

Zusammenfassung Bei Temperaturen zwischen 300 und 800 K wurde für einen breiten Konzentrationsbereich für x die spezifische Wärme von (Li_1–xK_x)₂SO₄-Mischkristallen untersucht und das entsprechende Phasendiagramm erstellt. Es wurde gezeigt, daß eine Änderung des Verhältnisses Li⁺:K⁺ auch das kritische Verhalten der spezifischen Wärme verändert. Die Ergebnisse werden hinsichtlich von Sreuungsmechanismen der Energieträger diskutiert.

     

Synthesis and NMR characterization of 6‐Phenyl‐6‐deoxy‐2,3‐di‐O‐methylcellulose

Cellulose ( 1 ) was converted for the first time to 6‐phenyl‐6‐deoxy‐2,3‐di‐O‐methylcellulose ( 6 ) in 33% overall yield. Intermediates in the five‐step conversion of 1 to­ 6 were: 6‐O‐tritylcellulose ( 2 ), 6‐O‐trityl‐2,3‐di‐O‐methylcellulose ( 3 ), 2,3‐di‐O‐methylcellulose ( 4 ); and 6‐bromo‐6‐deoxy‐2,3‐di‐O‐methylcellulose ( 5 ). Elemental and quantitative carbon‐13 analyses were concurrently used to verify and confirm the degrees of substitution in each new polymer. Gel permeation chromotography (GPC) data were generated to monitor the changes in molecular weight (DP_w) as the synthesis progressed, and the compound average decrease in cellulose DP_w was ～ 27%. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to characterize the decomposition of all polymers. The degradation temperatures ( °C) and percent char at 500 °C of cellulose derivatives 2 to 6 were 308.6 and 6.3%, 227.6 °C and 9.7%, 273.9 °C and 30.2%, 200.4 °C and 25.6%, and 207.2 °C and 27.0%, respectively. The glass transition temperature (T_g) of­6‐O‐tritylcellulose by dynamic mechanical analysis (DMA) occurred at 126.7 °C and the modulus (E′, Pa) dropped 8.9 fold in the transition from ?150 °C to + 180 °C (6.6 × 10⁹ to 7.4 × 10⁸ Pa). Modulus at 20 °C was 3.26 × 10⁹ Pa. Complete proton and carbon‐13 chemical shift assignments of the repeating unit of the title polymer were made by a combination of the HMQC and COSY NMR methods. Ultimate non‐destructive proof of carbon–carbon bond formation at C6 of the anhydroglucose moiety was established by generating correlations between resonances of CH₂6 (anhydroglucose) and C1′, H2′, and H6′ of the attached aryl ring using the heteronuclear multiple‐bond correlation (HMBC) method. In this study, we achieved three major objectives: (a) new methodologies for the chemical modification of cellulose were developed; (b) new cellulose derivatives were designed, prepared and characterized; (c) unequivocal structural proof for carbon–carbon bond formation with cellulose was derived non‐destructively by use of one‐ and two‐dimensional NMR methods. Copyright © 2002 John Wiley & Sons, Ltd.     

Nucleophilic substitution at the pyridine ring. Kinetics of the reaction of 2-chloro-3,5-dinitropyridine with arylthiolates in methanol

The reaction rates of 2-chloro-3,5-dinitropyridine 1 with a series of arylthiolates 2a-h in methanol have been measured at 25°C. The products are the corresponding 2-thioaryl-3,5-dinitropyridine 3a-h. Good Hammett correlation with ρ value −1.19 was obtained suggesting an elimination-addition mechanism S_NAr and the formation of Meisenheimer-like intermediates. Plot of log k₂ vs. pK_a values of arylthiols gave straight line with β=0.38 indicating that the π-bond breaking in the pyridine ring is so much advanced over bond making between the nucleophile and the carbon that bears the chlorine atom. Excellent correlation between log k₂ and log K (carbon basicity of arylthiolates) was obtained. © 1997 John Wiley & Sons. Inc. Int J Chem Kinet 29: 515–521, 1997.     

Coupled pore network model for the cathode gas diffusion layer in PEM fuel cells

Acta Mechanica Sinica - A pore network model (PNM) is developed for gas diffusion layer (GDL) in the cathode side of polymer electrolyte membrane fuel cells (PEMFCs). The model is coupled to...     

Impact of Coffee Bean Roasting on the Content of Pyridines Determined by Analysis of Volatile Organic Compounds

The aim of the study was to analyze the process of roasting coffee beans in a convection–conduction roaster (CC) without a heat exchanger and a convection–conduction–radiation roaster (CCR) with a heat exchanger for determination of the aroma profile. The aroma profile was analyzed using the SPME/GC-MS technique, and an Agrinose electronic nose was used to determine the aroma profile intensity. Arabica coffee beans from five regions of the world, namely, Peru, Costa Rica, Ethiopia, Guatemala, and Brazil, were the research material. The chemometric analyses revealed the dominance of azines, alcohols, aldehydes, hydrazides, and acids in the coffee aroma profile. Their share distinguished the aroma profiles depending on the country of origin of the coffee beans. The high content of pyridine from the azine group was characteristic for the coffee roasting process in the convection–conduction roaster without a heat exchanger, which was shown by the PCA analysis. The increased content of pyridine resulted from the appearance of coal tar, especially in the CC roaster. Pyridine has an unpleasant and bitter plant-like odor, and its excess is detrimental to the human organism. The dominant and elevated content of pyridine is a defect of the coffee roasting process in the CC roaster compared to the process carried out in the CCR machine. The results obtained with the Agrinose showed that the CC roasting method had a significant effect on the sensor responses. The effect of coal tar on the coffee beans resulted in an undesirable aroma profile characterized by increased amounts of aromatic volatile compounds and higher responses of Agrinose sensors.