Spectrophotometric determination of anthracycline anticancer agents with aluminum(III) and chromazurol S in a nonionic surfactant micellar medium.

A simple and highly sensitive spectrophotometric method for the determination of anthracycline anticancer agents, such as Daunorubicin hydrochloride (DAU), was established by using aluminum(III) and Chromazurol S (CAS) in a nonionic surfactant micellar medium. In the case of determination of DAU, the apparent molar absorptivity was 1.3 x 10(5) dm3 mol(-1) cm(-1) at 615 nm. Beer's law was obeyed in the concentration range of 0.028 - 2.82 microg ml(-1) for DAU. Owing to no need for solvent extraction, this method could be applied to assays of DAU and related drugs in pharmaceutical preparations.     

Polymerization of vinylcyclopropanes. III. Cationic polymerization of stereoisomers of 1-halo-2-vinylcyclopropanes

Vinylcyclopropane derivatives, 1-chloro- and 1-bromo-2-vinylcyclopropane, have respectively two stereoisomers, and radical polymerizations of both isomers gave 1,5-type polymers. On the other hand, only the cis isomers gave a polymer which had mainly 1,2-type structural units in cationic polymerizations with Lewis acids. The difference between the cationic polymerizabilities of the cis and trans isomers is interpreted in terms of steric conformation of monomers.     

Dynamics and thermodynamics of dimerization of parallel G-quadruplexed DNA formed from d(TTAGn) (n=3-5)

Parallel G-quadruplexes formed from oligonucleotide sequences, d(TTAGn), where n = 3-5, have been shown to form a dimer through end-to-end stacking of 3'-terminal G-tetrads. The monomers and dimers of the G-quadruplexes are in dynamic equilibrium with an exchange rate of approximately 1 s-1. A thermodynamic study demonstrated that the dimerization of the G-quadruplexes is largely enthalpic in origin.     

Laser-induced fluorescence of cyclohexadienyl (c-C6H7) radical in the gas phase

A laser-induced fluorescence spectrum was observed in the 500-560 nm region when a mixture of 1,4-cyclohexadiene and oxalyl chloride was photolyzed at 193 nm. The observed excitation spectrum was assigned to the A (2)A(2)<--X (2)B(1) transition of the cyclohexadienyl radical c-C6H7, produced by abstraction of a hydrogen atom from 1,4-cyclohexadiene by Cl atoms. The origin of the A<--X transition of c-C(6)H(7) was at 18 207 cm(-1). From measurements of the dispersed fluorescence spectra and ab initio calculations, the frequencies of several vibrational modes in both the ground and excited states of c-C(6)H(7) were determined: nu(5)(C-H in-plane bend)=1571, nu(8)(C-H in-plane bend)=1174, nu(10)(C-C-C in-plane bend)=981, nu(12)(C-C-C in-plane bend)=559, nu(16)(C-C-C out-of-plane bend)=375, and nu(33)(C-C-C in-plane bend)=600 cm(-1) for the ground state and nu(8)=1118, nu(10)=967, nu(12)=502, nu(16)=172, and nu(33)=536 cm(-1) for the excited states.     

Polymerization of vinylcyclopropanes. V. Radical copolymerization of 1, 1-dichloro-2-vinylcyclopropane with monosubstituted ethylenes

A peculiar copolymer composition equation applicable to the radical copolymerization of 1,1-dichloro-2-vinylcyclopropane with monosubstituted ethylenes was developed. The theory was applied to such ethylenes as methyl acrylate, methyl methacrylate, and styrene. The reactivity ratio parameters which give the best fit to the experimental data were determined.     

Creation and application of psychoactive designer drugs data library using liquid chromatography with photodiode array spectrophotometry detector and gas chromatography-mass spectrometry

In order to quickly confirm a potentially hazardous psychoactive designer drug (a compound in which part of the molecular structure of a stimulant or narcotic has been modified), we created a psychoactive drugs data library by performing analysis using liquid chromatography with photodiode array spectrophotometry (LC/PDA) and gas chromatography-mass spectrometry (GC/MS). The data in this library consist of the LC capacity factor (k′) ratios in relation to the internal standard, the ultraviolet (UV) spectra and the MS spectra of 104 compounds. By performing a comparative study of the data in this report with the analytical data for commercial and illegal drug products, it is possible to quickly identify the psychoactive designer drugs in 205 purchased products by using the library. Further, it is possible to analogize the structure of drugs for which there is no matching data in the library using similar data.Furthermore, when structural isomers of controlled substances have detected from the presented library, similarity of their biological effects on human will be predicted, thus leading to regulate their public circulation. Examples of these types of isomers include, for instance, the narcotic 3,4,5-trimethoxyamphetamine (TMA) and its positional isomers 2,4,5-trimethoxyamphetamine (TMA-2) and 2,4,6-trimethoxyamphetamine (TMA-6), or the narcotic 1-(3-chlorophenyl)piperazine (3CPP) and its isomers 1-(o-chlorophenyl)piperazine (2CPP) and 1-(p-chlorophenyl)piperazine (4CPP). Differentiation of these compounds is necessary in regulating them, and we report here the results of a study of a method to confirm these compounds using the present library.     

Preparation of monodispersed vinylpyridine–divinylbenzene porous copolymer resins and their application to high-performance liquid chromatographic separation of aromatic amines

For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 μm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine–divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine–divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine–divinylbenzene copolymer resins.     

Surface dilational moduli of polymer and blended polymer monolayers spread at air-water interfaces

Surface dilational moduli of polymer monolayers, blended polymer monolayers, and polymer particle monolayers spread at air–water interfaces are reviewed, focusing on measurements using surface pressure isotherm, surface pressure relaxation, and oscillating barrier methods. Differences between the surface dilational moduli of condensed polymer monolayers and expanded polymer monolayers are explored. Moreover, the features of the surface dilational moduli in blended polymer monolayers are discussed in terms of their miscibility.     

Theoretical analysis of correlation between ionization threshold fluence in IR‐MALDI and IR absorption spectrum of matrix molecules

To investigate the correlation between the wavelength dependence of ionization threshold fluence of target molecule in matrix‐assisted laser desorption/ionization by infrared (IR) laser and the IR absorption spectrum of matrix molecule, we have analyzed the IR absorption spectra of four matrix molecules using density functional theory and correlated ab initio molecular orbital method. The calculated IR absorption spectra of the isolated molecules showed more qualitative correlation with the wavelength dependence of ionization threshold fluence than those of the solid state structures. We can consider that a portion of matrix molecules lost the ordered crystal structure and that the transition to the diluted or isolated state occurred at the early process of IR laser irradiation. © 2012 Wiley Periodicals, Inc.