Ab initio studies of structural features not easily amenable to experiment. 17. The molecular structures of some strained cyclic hydrocarbons and estimates of their strain energies

The molecular structures of tricyclohexane, norbornane, quadricyclane, and cubane were completely refined by standard ab initio force relaxation on the 4-21G level. The results can be used as a basis to interpret some contradictory experimental reports found in the literature and to establish some hitherto unobserved structural trends involving the C? C and C? H bond distances of the cases studied. Group Delta;E values for C? (H)₃(C), C? (H)₂(C)₂, and C? (H)(C)₃ (Benson's notation) derived from the total energies of the completely relaxed 4-21G geometries of a number of unstrained hydrocarbons are also listed. The values are used to estimate the strain energies of the systems studied and of the optimized 4-21G geometries of cyclopropane, cyclobutane, cyclohexane, and bicyclo (2.1.0)pentane. Cooperative effects in the strain energies are discussed.     

Dual fluorescence (S1, S2) in chrysene and 3,4-benzophenanthrene

S₂ and S₁ fluorescence of chrysene and 3,4 benzophenanthrene has been observed in the vapour phase under collision free conditions. It is shown that the intermediate strong couplinng model can be applied to these molecules. The efficiency of the transfer of the excess energy to collision partners is given for different gases.     

Gaussian overlap approximation in the projected Hartree–Fock method

A method for the approximate calculation of matrix elements with respect to projected Hartree–Fock wave functions is proposed. The method is tested on some calculations in the many-parameter AMO method. It is found that the approximation reduces the amount of work, involved in the evaluation of the energy, by a factor of five and that it reproduces the exact values to within a few per cent.     

A potentiometric study of the water-soluble silver(I) complexes of n,n'-bis(2-hydroxyethyl)dithiooxamide : Part III. Determination of the different species

Silver(I) and N,N'-bis(2-hydroxyethyl)dithiooxamide (H₂X) in acidic solutions, form a series of water-soluble polynuclear complexes. These complexes can be represented by two general formulae: H_2qAg_pX_q and H_2q-1Ag_pX_q with q=1,2,3 and p=q, q-1.     

Spectroscopic evidence for the intermediacy of a 6-R-2,4-diazabicyclo-[3.1.0]hex-2-(3)ene in the photoisomerization of 4-R-1,4-(3,4)-dihydropyrimidines

¹H- and ¹³C-nmr spectroscopy is presented showing that photolysis of 4-(p-trifluoromethylphenyl)-1,4-(3,4)-dihydropyrimidine yields 6-(p-trifluoromethylphenyl)-2,4-diazabicyclo[3.1.0]hex-2-(3)ene.     

The determination of all the platinum group elements and gold in rocks and ore by neutron activation analysis after preconcentration by a nickel sulphide fire-assay technique on large samples

The noble metals are inhomogeneously distributed in sulphide ores and their host rocks. It is therefore necessary to analyse large sample sizes to obtain representative analyses. A nickel sulphide fire assay technique has been adapted to extract the noble metals from a large sample size (50 g) into a nickel sulphide button. Subsequently the fire assay button is dissolved in hydrochloric acid and the solution is filtered. The noble metal residue retained on the filter paper is analysed quantitatively by i.n.a.a. techniques. This method is rapid, relatively inexpensive and has better sensitivities for all the noble metals than other analytical techniques.     

Investigations on the conditional kinetic and thermodynamic stability of aquatic humic substance-metal complexes by means of EDTA exchange, ultrafiltration and atomic spectrometry

The conditional metal availability and the kinetic stability of humic substance-metal species in humic-rich waters (e.g. bog water) was characterized by means of EDTA exchange. For this purpose a combined procedure consisting of time-controlled ligand exchange by EDTA, species differentiation by a fast single-stage tangential-flow ultrafiltration (TF-UF) technique (cut-off 1 kDa) and sensitive atomic spectrometry methods (e.g. AAS, ICP-OES, TXRF) was developed. The kinetics and the yield of the EDTA exchange served as operational parameters for assessing the kinetic stability and EDTA availability of HS-metal species, respectively. Considerable fractions of natural HS-metal species studied were shown to be EDTA-inert (e.g. 31% of the total Fe, 44% of the total Al) even after long reaction times (48 h), in contrast to artificial ones formed in solutions of isolated HS. Moreover, the conditional thermodynamic stability of HS-metal complexes formed by successive loading of an aquatic reference HS (HO14) with a number of heavy metal ions (e.g. Cr(III), Cu(II), Fe(III), Mn(II), Zn(II)) was also evaluated discriminating the free metal concentrations by means of TF-UF. In addition, from the loading isotherms obtained conditional complexation capacities could be derived for the studied HS exhibiting the order Fe(III)>Cu(II)>Cr(III)>Co(II)>Mn(II).     

The molecular structure of cis- and trans-1,2-difluoro-ethene: An electron diffraction study

The molecular structure of cis- and trans-1,2-difluoroethene was studied in the gas phase by electron diffraction, using the sector-microphotometer technique. The molecules are planar. For trans-difluoroethene the geometrical parameters are: C-F bond: 1.338(0.003) Å; CC bond: 1.320(0.009) Å; C-H bond: 1.088(0.004) Å, ∠CCF 119.8°(0.2°); ∠CCH: 125° (1.2°). For cis-difluoroethene: C-F bond: 1.332(0.003) Å; CC bond: 1.311(0.008) Å; C-H bond: 1.100(0.003) Å; ∠CCF: 122.5°(0.2°); ∠CCH:127.0 °(2.3°).     

Purification of adipoyl-7-amino-3-deacetoxycephalosporanic acid from fermentation broth using stepwise elution with a synergistically adsorbed modulator

Multicomponent adsorption data of a fermentation broth containing adipoyl-7-amino-3-deacetoxycephalosporanic acid (adipoyl-7-ADCA), a cephalosporin precursor for 7-ADCA, and two key impurities, alpha-hydroxyadipoyl-7-ADCA and alpha-aminoadipoyl-7-ADCA were obtained from batch equilibrium and frontal chromatography tests. Amberlite XAD-1600 was chosen as the resin. A rate model was applied to simulate the chromatograms. An alkaline buffer, which by itself has no affinity for the resin, was used as the eluent. The widely used reversed-phase modulator model is inaccurate in explaining the stepwise elution data. A new model, the induced competition model, has been developed to account for apparent retention of the buffer in the presence of adsorbed species. Close agreement between the simulations and the data was achieved with the new model.