Rejuvenating old computerized spectrometric instrumentation: discussion of two case histories

Computerized analytical instruments of late 70's and 80's are facing rapid technological obsolescence, although they are often retaining good analytical performances. Responsibility is to be attributed to the fast advance in computer technology, which is leaving little or no back-compatibility with old standards and data formats. Rejuvenation may be reached by simple hardware and software modifications, to allow data exchange with modern PC's and LIMS. Two typical case histories for spectrometric instrumentation of late 70's are then presented and discussed in a general fashion.     

The microwave spectrum and dipole moment of 1,1-diflurobenzocyclopropene

The rotational spectrum of 1,1-difluorobenzocyclopropene, measured in the X- and R-bands, has been analysed to give the rotational constants in the ground and first four vibrational states. These constants are in agreement with a structure based on those of crystallographically determined related molecules. Indirect evidence is adduced that the carbon skeleton is indeed planar. The dipole moment in the ground (3.57₂ ± 0.02 D) and first excited state (3.54 ± 0.03 D) has been determined through an analysis of the second-order Stark effect. This high value implies considerable polarisation of the π-electron framework.     

Reference value standards for pH measurements in 10, 30, 50, and 70% (w/w) 2-propanol/water solvent mixtures at temperatures from 288.15 to 318.15 K

Reference value standards, pH (RVS), for 0.05 mol kg^?1 potassium hydrogenphthalate (KHPh) reference buffer solutions in 10, 30, 50 and 70% (w/w) 2-propanol/water solvent mixtures at temperatures from 288.15 to 318.15 K are determined from reversible e.m.f. measurements of the cell Pt¦H₂¦KHPh + KCl¦AgCl¦Ag¦Pt. The consistency of the present results is confirmed by multilinear regression analysis of the pH values obtained for each solution composition and temperature, allowing appropriate interpolation of pH (RVS) values within the range of the experiment. The ancillary values of the standard e.m.f. of the cell Pt¦H₂¦HCl¦AgCl¦Ag¦Pt are optimized through multilinear regression analysis of the available data in the literature, and the ancillary values of the first ionization constant of o-phthalic acid (H₂Ph; benzene-1,2-dicarboxylic acid) in these solvent mixtures are evaluated from reversible e.m.f. measurements of the cell Pt¦H₂¦H₂Ph + KHPh + KCl¦AgCl¦Ag¦Pt.     

Accurate mass measurement of synthetic analogues of prazosine by matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry (MALDI-TOFMS) has been investigated as a tool for accurate determination of the molecular mass of synthetic analogues of prazosine, a molecule used for the treatment of hypertension. Samples were dissolved in methanol, mixed with mass calibration standards, and crystallised on the target with alpha-cyano-4-hydroxycinnamic acid as matrix. Acquisition of spectra was rapidly completed in reflectron mode, allowing high resolution (6000-10000) and sensitive (about 1-10 pmol of sample on target) determination of the synthetic products. The results show the effectiveness of MALDI-TOFMS for accurate mass determination of these fairly large molecules, which are otherwise difficult to analyse by other high-resolution mass spectrometric techniques.     

Analytical characterization of municipal solid waste incinerator fly ash. Part II

The synergy of the micro FT-IR (Fourier Transform-Infrared) and SEM-EDX (Scanning Electron Microscopy-Energy Dispersive X-ray) techniques has been shown to be particularly helpful and effective for the characterization of inorganic compounds in fly ashes. The experimental data obtained by these techniques have been interpreted in comparison with those of other techniques. The presence of calcium carbonate, some sulfates, ammonium nitrate, calcium hydrogen phosphate, some chlorides, some oxides and aluminium silicates have been verified.     

Poly(ethylene glycol)-supported tetrahydroxyphenyl porphyrin: a convenient,recyclable catalyst for photooxidation reactions

[reaction: see text] A new poly(ethylene glycol)-supported porphyrin has been prepared and its ability as a promoter in photooxidation reactions has been studied. The PEG-supported catalyst exhibits high activity, comparable to that of a nonanchored sensitizer, and it is easily removable by filtration from the reaction mixture. The polymer-bound porphyrin has been recycled up to six times with no loss of chemical and stereochemical efficiency.