Mass spectrometry of 3,4-dihydroquinazolin-4-ones of pharmaceutical interest. Part 3 . Electron ionization mass spectra of 2-substituted-3-(5′-pyrazolyl)-4(3H)-quinazolinones

The fragmentation reactions induced by electron impact of eighteen title compounds has been investigated with the aid of low beam energy spectra (14 eV, nom. value), metastable ion detection, high resolution measurements and labelling experiments. The loss of the 4-carbonyl oxygen together with the 3-substituent, which constitutes a characteristic fragmentation route of 3-aryl and 3-heteroaromatic substituted-4(3H)-quinazolinones, is again observed, but the presence of a carboxyethyl group at the 4′-position of the pyrazole ring is responsible of an anomalous loss of 47 daltons from the molecular ion. Lastly, a comparison with the previously described behaviour of 3-(5′-isoxazolyl) derivatives was carried out.     

Depolymerization of water soluble coal polymer from subbituminous coal and lignite by lignin peroxidase

Coal polymers, water soluble at pH 3.5, were prepared from North Dakota lignite and German subbituminous coal in 35–61% yield. Gel permeation chromatography showed a major component of relatively narrow molecular weight range >75,000. The material did not dialyze through a 12,000-14,000 MW cutoff membrane under several conditions. Minor amounts of smaller fragments were present, but monomeric components were not detected. Incubation of soluble polymer with lignin peroxidase ofPhanerochaete chrysosporium caused substantial disappearance of the high molecular weight polymer and formation of smaller amounts of both higher and lower molecular weight components, but not of monomeric compounds. Addition of veratryl alcohol enhanced depolymerization. Coal polymer competitively inhibited veratryl alcohol oxidation by lignin peroxidase.

     

1H-NMR,Ultraviolet and infrared spectra of some (Z)-α-(phenyl)-β-(2-furyl), -(2-pyrrolyl) and -(N-methyl-2-pyrrolyl)acrylonitriles

The ¹H-nmr data of some (Z)-α-(p-substituted-phenyl)-β-(2-furyl), -(2-pyrrolyl), and -(N-methyl-2-pyrrolyl)-acrylonitriles have been investigated to indicate the preferred conformation and to establish the conformational preferences of the β-heterocyclic ring. The ultraviolet spectra have been discussed in order to obtain information about the chromophores responsible for the absorption. The infrared spectra have been analyzed for the identification of the main absorption frequencies of cyano and ethylenic groups and to assign the characteristic absorption bands to specific normal vibrations of the heteroaromatic nuclei.     

Routine determination of major anions in atmospheric aerosols by capillary electrophoresis

Capillary electrophoresis (CE) with indirect UV detection utilizing a pyromellitate-based electrolyte was used for the routine analysis of major anions in atmospheric aerosols collected on filters with high-volume (Hi-Vol) samplers. The long-term reliability of the CE system was checked over an 8-month period during which over 2900 samples were analyzed. In addition, approximately 1100 samples were analyzed in parallel by ion chromatography (IC). It has been shown that acceptable analytical performance can be routinely obtained. The agreement between the CE and IC results is good, generally better than 20% at concentrations larger than 1 mg l⁻¹.     

Characterization of cocoa butters and other vegetable fats by pyrolysis-mass spectrometry

Pyrolysis Mass Spectrometry (Py-MS) was used for the discrimination of cocoa butters from other vegetable fats. Mass spectra ranging from 50 amu to 250 amu were analyzed by principal component analysis (PCA) and with neural nets. The application of neural nets leads to a good discrimination between the two classes. Detailed analysis of the nets revealed that only the first 60 masses were used within the net. The use of PCA requires a careful selection of the number of masses included in the calculation. Canonical variance analysis was applied to determine the significant masses. Optimal performance of PCA was observed only using the first 22 significant masses. Most of these masses were different from the ones used by the neural net. It seems that the mass spectra obtained by Py-MS contain sufficient information for the discrimination of pure cocoa butter from other vegetable fats, but none of the methods seems to be able to extract all information available. Neural net provides a very robust method for this task and no prior data selection was necessary. Received: 13 May 1996 / Revised: 7 August 1996 / Accepted: 7 August 1996     

Determination of thallium and lead in cadmium salts by anodic stripping voltammetry with addition of surfactants to suppress the cadmium peaks

Conditions have been found which make possible the determination of thallium and/or lead in cadmium and its salts without preliminary separation. The electrochemical activity of the cadmium, which usually interferes in the determination of thallium, is inhibited by the addition of 0.01% of polyethylene glycol of M.W. 4000. Thallium is determined by electrolysis at ?0.74 V vs. SCE, in 0.1M EDTA solution: 10^?1M thallium can be determined in the presence of 0.1M cadmium, while copper and lead at 10^?2M and 10^?5M respectively do not interfere. Lead is determined in 0.1M acetic acid containing 0.1% cetyltrimethylammonium bromide (CTAB). The addition of CTAB shifts the cadmium peak, as well as the optimum deposition potential for cadmium, to more negative values, making it possible to determine lead in the presence of cadmium as long as the deposition potential lies in the range between ?0.50 and ?0.56 V vs. SCE. Lead can be determined in the presence of ten times as much thallium.     

Charge transfer across a polymer gel/liquid interface: determination of ionophores

An electrochemical method for the determination of the ionophores monensin and lasalocid was developed, based on the polarization of an agar gel/nitrobenzene electrolyte interface. The measured current corresponding to the facilitated ion transfer across this interface is directly proportional to the concentration of an ionophore dissolved in the organic phase. Using cyclic voltammetry in a three-electrode system the detection limit for both ionophores is about 3 × 10^?5 M.     

New membrane materials for potassium-selective ion-sensitive field-effect transistors

Several polymeric materials were studied as membrane materials for potassium-selective ion-sensitive field-effect transistors (ISFETs) to overcome the problems related with the use of conventional plasticized poly(vinyl chloride) membranes casted on ISFET gate surfaces. Several acrylate materials, such as ACE, Epocryl and derivatives, showed no reproducible results. Three room-temperature vulcanizing (RTV)-type silicone rubbers were tested. The addition-type RTV-2 silicone rubber was not suitable as a membrane material, but the condensation-type RTV-1 and especially the RTV-2 silicone rubber showed good results. ISFETs with a Silopren membrane showed a durability of at least 2 months.     

Gels of hydrophobically modified ethyl(hydroxyethyl) cellulose cross-linked by amylose: effects of hydrophobe architecture

Previous work has shown that amylose (AM) can cross-link hydrophobically modified polymers by inclusion complexation, whereby thermoreversible cold-setting gels are formed. Here we investigate the complexation of AM with different samples of hydrophobically modified ethyl(hydroxyethyl) cellulose (HMEHEC), distinguished by differences in the architecture of the hydrophobes (the hydrophobic side chains). All hydrophobes, except one, were based on linear alkyl chains, but with varying chain lengths (C12-C14). In addition, some samples contained short hydrophilic "spacers", consisting of 2-5 ethylene oxide units, between the alkyl chains and the EHEC backbone. Gels of varying strength were obtained for the different AM/HMEHEC samples. The alkyl chain length seemed to be the major factor affecting the gel strength, with longer alkyl chains giving stronger gels. For similar alkyl chain lengths, stronger gels were obtained when a spacer was present. Addition of AM caused a small increase of the cloud points of HMEHECs with C14 hydrophobes in water. Time-dependent effects and effects of the sample preparation procedure were also investigated. The reversibility of the gelation with respect to shear was confirmed. A gel destroyed by added surfactant was shown to reform on removal of the surfactant by dialysis.     

Relaxation processes of the liquid crystal ME6N in the isotropic phase studied by Raman scattering experiments

We have investigated the Raman profiles of the nu(C[Triple Bond]N) and nu(C=O) vibrational modes of the nematic liquid crystal ME6N (4-cyanophenyl-4(')-hexylbenzoate) in the isotropic phase at different temperatures and used them as probes of the dynamics and structural organization of this liquid. The vibrational time correlation functions of the nu(C[Triple Bond]N) mode, rather adequately interpreted within the assumption of exponential modulation function (the Kubo-Rothschild theory), indicate that the system experiences an intermediate dynamical regime that gets only slightly faster with increasing temperature. However, this theory fails in predicting the non-exponential behavior that the time correlation functions manifest in the long time range (t>3 ps). For this reason we have additionally approached the interpretation of vibrational correlation functions in terms of the theory formulated by Rothschild and co-workers for locally structured liquids. The application of this theory reveals that the molecular dynamics in this liquid crystal in the isotropic phase is that deriving from a distribution of differently sized clusters, which narrows as the temperature increases. Even at the highest temperature reached in this study (87 degrees C above the nematic-isotropic transition), the liquid has not yet achieved the structure of the simple liquid and the dynamics has not reached the limit of the single channel process. The vibrational and orientational relaxations occur in very different time scales. The temperature independence of the orientational dynamics in the whole range from 55 degrees C to 135 degrees C has been referred to the nonhydrodynamic behavior of the system, arising when local pseudonematic structures persist for times longer than the orientational relaxation. The occurrence of the process of resonant vibrational energy transfer between the C=O groups of adjacent molecules has been revealed in the isotropic phase by a slightly positive Raman noncoincidence effect in the band associated with the nu(C=O) mode. A qualitative interpretation is tentatively given in terms of partial cancellation of contributions deriving from structures having opposite orientations of their C=O groups.