Separation and quantitation of components in FD&C Red No. 3 using capillary electrophoresis

The use of capillary electrophoresis as a technique to separate and quantitate components of FD&C Red No. 3 (erythrosine, color index No. 45430) is described. The fluorescein isomers, 2',4',5'-triiodofluorescein (2,4,5-I3F) and 2',4',7'-triiodofluorescein (2,4,7-I3F), the most abundant by-products formed during the preparation of the dye, were selected for quantitation studies. The separation of other lower halogenated impurities was also demonstrated. Electrophoretic mobility of the compounds was achieved in a 50 mM borate, 25 mM sodium dodecyl sulfate buffer at pH 9.3. The limits of quantitation were found to be 0.15% (w/w) (2,4,5-I3F) and 0.14% (w/w) (2,4,7-I3F) (relative to the mass of FD&C Red No. 3). The method is linear from 0.08 to 20.0% (w/w) for 2,4,5-I3F and between 0.06 and 17.0% (w/w) for 2,4,7-13F. In addition, relative standard deviations of 2.03 and 5.11% were determined from precision studies in the repeat analysis of FD&C Red No. 3 for 2,4,5-I3F and 2,4,7-I3F, respectively. Overall, the CE method produced data in excellent agreement with the reference HPLC method, used considerably less solvent and sample, generated less waste and was found to be considerably more cost efficient.     

Chemo-enzymatic synthesis of 4-methylumbelliferyl beta-(1-->4)-D-xylooligosides: new substrates for beta-D-xylanase assays

Transglycosylation catalyzed by a beta-D-xylosidase from Aspergillus sp. was used to synthesize a set of 4-methylumbelliferyl (MU) beta-1-->4-D-xylooligosides having the common structure [beta-D-Xyl-(1-->4)]2-5-beta-D-Xyl-MU. MU xylobioside synthesized chemically by the condensation of protected MU beta-D-xylopyranoside with ethyl 2,3,4-tri-O-acetyl-1-thio-beta-D-xylopyranoside was used as a substrate for transglycosylation with the beta-D-xylosidase from Aspergillus sp. to produce higher MU xylooligosides. The structures of oligosaccharides obtained were established by 1H and 13C NMR spectroscopy and electrospray tandem mass spectrometry. MU beta-D-xylooligosides synthesized were tested as fluorogenic substrates for the GH-10 family beta-D-xylanase from Aspergillus orizae and the GH-11 family beta-D-xylanase I from Trichoderma reesei. Both xylanases released the aglycone from MU xylobioside and the corresponding trioside. With substrates having d.p. 4 and 5, the enzymes manifested endolytic activities, splitting off MU, MUX, and MUX2 primarily.     

Methyl displacements from cyclopentadienyl ring planes in sterically crowded (C5Me5)3M complexes

The displacements of the methyl substituents away from the metal and out of the cyclopentadienyl ring plane are compared in sterically crowded (C(5)Me(5))(3)M complexes vs sterically normal f-element complexes in an attempt to evaluate the utility of this parameter in predicting unusual (C(5)Me(5))(1-) ring reactivity. The out-of-plane displacements of 16 sterically crowded tris(cyclopentadienyl) complexes of general formula (C(5)Me(5))(3)M, (C(5)Me(4)R)(3)M (R = Et, (i)Pr, (t)()Bu, SiMe(3)), (C(5)Me(5))(3)MX (X = anion), and (C(5)Me(5))(3)ML (L = neutral ligand) are compared with [(C(5)Me(5))(2)U](2)(C(6)H(6)), (C(5)Me(5))(2)Sm(PC(4)H(2)(t)Bu(2)), and 33 representative examples of f-element bis(cyclopentadienyl) complexes with normal cyclopentadienyl behavior and coordination numbers ranging from 6 to 10. In general, the methyl displacement values of sterically crowded complexes overlap with those in the other complexes, which demonstrates that the basis of the structural distortions is complex. However, if the most extreme out-of-plane displacement in each of the sterically crowded complexes is examined vs the analogous maximum out-of-plane displacement in less crowded systems, there appears to be a basis for predicting cyclopentadienyl reactivity.     

Conformational equilibria and photoinduced tautomerization in 2-(2′-pyridyl)pyrrole

Depending on the polarity and protic abilities of the solvent, 2-(2′-pyridyl)pyrrole can exist in either syn or anti rotameric forms. In nonpolar solvents, intramolecular excited state single proton transfer is observed, manifested by the appearance of low-energy tautomeric emission. The solvent-assisted excited state double proton transfer reaction is also detected. DFT calculations confirm low barriers for both single and double proton transfer processes in the lowest excited singlet state and show different character of the tautomerization in both cases: in the intramolecular reaction, mutual approach of two nitrogen atoms plays an important role.     

Polystyrene prepared by reactive extrusion: kinetics and effect of processing parameters

The conversion and residence time were investigated during the bulk polymerization of styrene in a twin screw extruder. It was found that polymerization mainly occurred in the zone between 400 and 1000 mm along the screw axis in the extruder, corresponding to the residence time of the reactants ranging from 1 to 4 min in the extruder. Furthermore, the processing conditions (feed rate, screw rotation rate) and average molecular weight of the polymer have a great effect on the residence time. Based on dimensionless analysis, a model of the residence time has been built‐up, which has been confirmed by the results of realistic measurements. A kinetic model of the polymerization has also been established under the assumption that the screw extruder can be regarded as an ideal plug flow reactor. Copyright © 2004 John Wiley & Sons, Ltd.     

Catalytic activity of silica in ozone formation in electrical discharges

The catalytic action of granular silica packing on ozone formation has been observed under discharge conditions. Using a glass ozonizer with a metal high-voltage electrode, at a frequency of 400 Hz it was possible to obtain much higher ozone concentrations in the presence q( silica than without packing, with the same total energy consumption. The dependence between ozone production and energy efficiency is considered, and conditions of the optimum ozonizer run are discussed. It is shown that in the all-glass ozonizer with a narrow discharge gap, the ozone concentration may be as high as 6.5% (ca. 130g O₃/m³) when silica packing is applied.     

Synthesis of fused purinoquinazolines. Three new heterocyclic ring systems

The Ullmann reaction of 8-aminotheophylline or 8-aminocaffeine with 2-chlorobenzoic acid and of 8-bromotheophylline with ethyl-2-aminobenzoate afforded derivatives of three new heterocyclic systems: purino[7,8-α]quinazoline-5,9,11(6H,8H,10H)-trione, purino[8,9-b]quinazoline-2,4,11(1H,3H,5H)-trione and purino[8,7-b]quinazoline-2,4,6(1H,3H,11H)-trione, respectively.     

Automatic analysis of mixed spectra : Generalised spectral subtraction applied to electron spin resonance spectroscopy

A new technique is described for estimating the pure component spectra from a set of linearly independent spectra. The process is one of generalised spectral subtraction in which an iterative combination of multivariate linear least-squares analysis and matrix transformation is applied to the input data to give estimates of the number of independent components in the original mixed spectra. This technique is applicable to bipolar data (e.g. from e.p.r. spectra) as well as absorption spectra determined by any spectroscopic technique, provided that the spectra may be reasonably assumed to be an additive mixture of unknown pure components. Numerical model examples are given together with an experimental application to electron spin resonance.     

Biosynthesis of aglajnes, polypropionate allomones of the opisthobranch mollusc Bulla striata

The biogenesis of aglajnes, polypropionate allomones of the cephalaspidean mollusc Bulla striata, has been investigated in vivo by feeding experiments. Incorporation of the committed precursor, [1-¹⁴C]-propionate, into aglajne-1 (1) and -3 (3) established the de novo origin of these compounds in B. striata. In the letter we also discuss briefly the ecological meaning of the origin of polypropionates in B. striata and in other cephalaspidean molluscs.     

Synthesis of Glycosylrifamycins,a new type of semisynthetic rifamycins

Glycosylrifamycins, a new type of semisynthetic rifamycin derivatives, can be easily obtained by reaction of 3-(2-aminoethylthio)rifamycin SV ( 2 ) with a glycosyl compound carrying a coupling group, such as isothicyanate or carboxy. We prepared O-acetylated and free glucopyranosyl and arabinopyranosyl derivatives of rifamycin S and SV (see 3–10 ). Additionally, derivatives with D -saccharo-1,4-lactone and with shikimic acid were obtained (see 11–15 ). Glycosylrifamycins show an interesting inhibitory power on Gram-positive bacteria (Table).