A study of simultaneous photolysis and photoaddition reactions of riboflavin in aqueous solution

The photodegradation reactions of riboflavin (RF) in the presence of 0.05-2.00 M phosphate (pH 7.0) have been studied using a specific multicomponent spectrophotometric method. The reactions involve simultaneous photolysis (intramolecular photoreduction) and photoaddition (intramolecular photoaddition) leading to lumichrome (LC) and cyclodehydroriboflavin (CDRF), respectively, as major products. The contribution of each reaction in the overall photodegradation depends upon the phosphate concentration, i.e., higher the phosphate concentration higher the extent of photoaddition. The apparent first-order rate constants for the photodegradation of RF and for the formation of LC and CDRF at 0.25-2.00 M phosphate concentration range from 0.65 to 3.03 x 10(-2), and from 0.41 to 0.99 x 10(-2) and 0.12 to 1.63 x 10(-2) min(-1), respectively. The second-order rate constants for the phosphate catalysed photodegradation of RF and for the formation of LC and CDRF are 2.12 x 10(-4) and 0.61 x 10(-4) and 1.41 x 10(-4) M(-1)s (-1), respectively. Since the formation of CDRF by photoaddition is catalysed by HPO(4)(2-) ions, it is suggested that H(2)PO(4)(-) ions may be involved in the formation of LC by photolysis. Thus, both H(2)PO(4)(-) and HPO(4)(2-) ions may catalyse the two major reaction pathways of riboflavin photodegradation, respectively.     

Ab initio and variational transition state approach to beta-C3N4 formation: kinetics for the reaction of CH3NH2 with H

The CH3NH2 molecule has been considered as either an important intermediate in methane and ammonia mixtures or a precursor in methylamine and hydrogen mixtures in the synthesis of carbon nitride thin films. The fast Hydrogen (H) abstraction from CH3NH2 is an important process involved in the formation of HCN or CNH in the chemical vapor deposition (CVD) of carbon nitride thin films. The energetic and kinetic characteristics of the H abstraction reaction from CH3NH2 by atomic H used in CVD of beta-C3N4 were studied using ab initio direct dynamics methods for the first time. Two primary processes were identified for this reaction: H abstraction from the CH3 group and H abstraction from the NH2 group. On the basis of ab initio data, the rate constants of each channel have been deduced by canonical variational transition state theory with small-curvature tunneling correction over a wide temperature range of 200 to approximately 3000 K. The theoretical results were compared with available experimental data.     

High pressure Raman studies of 7,7,8,8-tetracyanoquinodimethane (TCNQ) and CuTCNQ

The high-pressure Raman studies of 7,7,8,8-tetracyanoquinodimethane (TCNQ) single crystals and polycrystalline CuTCNQ are presented in this paper. TCNQ shows a phase transition at 22 kbar, a pressure higher than reported earlier. CuTCNQ undergoes a first order phase transition at 30 kbar, which is characterized by the abrupt disappearance of all the Raman bands.     

Single-sweep polarography of the copper(II)-3-hydroxy-1-p-sulphonatophenyl-3-phenyltriazene complex and its analytical applications

A polarographic investigation of the copper-3-hydroxy-1-p-sulphonatophenyl-3-phenyltriazene (HSPT) complex in 0.05 M sodium tetraborate medium is described and a simple and sensitive single-sweep polarographic method for the determination of trace amounts of copper in biological samples is proposed. The complex was shown to be Cu(HSPT)2 with log beta' = 11.38. The polarographic wave is caused by the reduction of copper(II) in the adsorbed complex to copper amalgam on the surface of a mercury electrode. The current peak is directly proportional to the concentration of copper in the range 8.0 x 10(-9)-4.0 x 10(-6) M and the detection limit is 5.0 x 10(-9) M.     

Reaction of Cα,O-dilithiooximes with functionalized carbonyl compounds. Part 2 . Reaction with α-chloroketones and α,β-unsaturated aldehydes and ketones

The reaction of Cα,O-Dilithiooximes 2 and α-chloroketones afforded 5-(hydroxymethyl)-Δ²-soxazolines 4 . α,β-Unsaturated aldehydes and ketones reacted with 2 to give the corresponding acyclic 1,2-addition products 5 . The latter were cyclized with phosphorus pentoxide to 5-vinyl-Δ²-isoxazolines 6 .     

Determination of tripolyphosphate in frozen cod and scallop adductor by ion chromatography

We introduce a method for the determination of tripolyphosphate in frozen cod and scallop adductor by using ion chromatography. The tripolyphosphate was extracted from minced cod and scallop adductor with deionized water by ultrasonic leaching, and then the proteins soluble in water were precipitated with trichloroacetic acid and removed by filtering. An ion chromatograph with an ionpac AS11-HC anion-exchange column, an ASRS (Anion Self Regenerating Suppression), a conductivity detector and a gradient pump (sodium hydroxide gradient) was used. The detection limit was below 5 mg tripolyphosphate/kg cod or scallop adductor. This method is applicable to the determination of polyphosphates in aquatic products and the procedures are easy to implement.     

Monitoring of mutagenic process with piezoelectric quartz crystal impedance analysis

A novel method for monitoring of mutagenic process of dimethyl sulfate to Salmonella typhimurium strain (TA100) was proposed by using piezoelectric quartz crystal impedance (PQCI) analysis technique. The time courses of responses piezoelectric impedance parameters for a quartz crystal in a culture system were simultaneously obtained and discussed. It was found that the motional resistance variation (DeltaR(m)) increases and frequency shift (Deltaf) of PQC sensor decreases correspondingly during the mutagenic process of the bacteria. These parameters could reflect the variations of viscosity and density of culture system. By fitting DeltaR(m) versus time curves toward Gompertz bacterial growth model, we obtained and discussed the bacterial growth parameters for both normal growth and mutagenic process. The experiments showed that the proposed method could provide real time and multidimensional impedance information to the monitoring of mutagenic process.     

<Emphasis Type="Italic">Ab initio</Emphasis> study of small coinage metal telluride clusters Au<Subscript>n</Subscript>Te<Subscript>m</Subscript> (<Emphasis Type="Italic">n,m</Emphasis> = 1, 2)

The geometries of the most stable isomers of gold telluride systems AuTe, Au₂Te, and AuTe₂ are determined using the MP2 method. The aspect of gold—telluride interaction, the electron correlation, and relativistic effects on geometry and stability are investigated at the MP2 and CCSD(T) theoretical levels. The results show that the electron correlation and relativistic effects are responsible not only for gold—gold attraction but also for additional gold—telluride interaction. The gold—telluride interaction is strong enough to modify the known pattern of bare gold clusters. Both effects are essential for determining the geometry and relative stability of this type of systems.     

Optimization of the Synthesis of 2,6–Dinitro-4-trifluoromethylphenyl Ether Substituted Cyclodextrin Bonded Chiral Stationary Phases

The comparisons of five different chiral stationary phases (CSPs) based on 2,6-dinitro-4-trifluoromethylphenyl (DNP-TFM) ether substituted β-cyclodextrin are presented. The five CSPs differ from each other in the linkage/spacer chemistry, or on the position of the substituents on β-cyclodextrin, or in the sequence of the synthetic procedure. The results show that there are two optimum combinations: (1) DNP-TFM randomly substituted on the β-cyclodextrin as the chiral selector along with a carbamate linkage chain bonding it to the silica support; and (2) β-cyclodextrin derivatized by DNP-TFM substituents only on the C-2 and C-3 positions of the cyclodextrin with an ether linkage chain anchoring it to the silica gel. These two combinations show complementary separations for some enantiomers. The spacer chain effect is much more pronounced for the CSP based on the β-cyclodextrin derivatives with DNP-TFM substituents only on C-2 and C-3 positions than its randomly substituted counterpart. The sequence of derivatizing the cyclodextrin and attaching it to silica gel also affects its selectivity and efficiency. The β-cyclodextrin should be derivatized before it is linked to the silica gel.     

Analysis of Zoledronic Acid and Its Related Substances by Ion-Pair RP-LC

A simple high-performance liquid chromatographic method – ion-pair reversed- phase high performance liquid chromatography (RPIC) has been developed and employed for the analysis of zoledronic acid and its related substances in bulk material and commercial dosage forms. The mobile phase was a mixture of methanol (20%) and 5 mmol L^–1 phosphate buffer (80%) containing 6 mmol L^–1 tetrabutylammonium bromide, adjusted to pH 7.0 with sodium hydroxide. C₈ column was used as the stationary phase. The chromatographic conditions were optimized. The active ingredient – zoledronic acid was successfully separated from its related substances, including remained imidazol-1-yiacetic acid in the synthesis of zoledronic acid and other possible impurities of oxidation and decomposition. The excipients did not interfere with the determination of zoledronic acid in commercial dosage formulations. The method was rapid, simple, accurate and reproducible. It was not only successfully employed for the assay of zoledronic acid in bulk material and pharmaceutical dosage forms but also for the determination of its related substances.