Variation of calculated single bond lengths in saturated hydrocarbon and silicon hydride molecules

A series of saturated X_nH_m (X being either C or Si) molecules is studied using the MINDO /3 and MNDO quantum-chemistry procedures. We find that the proximity of H atoms tends to shorten X? X bonds, and that this effect is (especially for MINDO /3) much larger than a similar trend in experimental values. The connection between this and hybridization values calculated from localized orbitals is investigated. It is found that the hybridization model works well for X? H bonds, whereas for X? X bonds non-σ-bond effects also play a significant role. It is shown that the changes in electronic structure may be directly connected to differences in X and H atomic levels, so that similar bond length differences may be expected in other molecular orbital calculations.     

The mass spectra of 2-alkyl N-methyl pyrrolidines

The mass spectra of a series of 2-alkyl N-methyl pyrrolidines have been examined and fragments which may be pyrrole type structures are apparent. These ions are most prominent in the spectra of the long chain alkyl derivatives.     

Flow-injection determination of nonylphenol in liquid media using a piezoelectric immunosensor

A piezoelectric flow immunosensor for the rapid determination of nonylphenol in aqueous solutions was developed. An aminophenol-protein conjugate (4-AP-GA-BSA) immobilized on the presilanized surface of a silver electrode was used as a bioreceptor coating of the sensor. The effects of the nature and concentration of monoclonal and polyclonal antibodies on the analytical signal of the sensors were studied; the activity of immunoreagents was evaluated based on the binding constants K _b. The cross reactions of various phenols with antibodies were studied and the cross reaction percentages were found. A procedure for the flow-injection determination of nonylphenol in liquid media was developed using a piezoelectric immunosensor as a detector. The calibration graph was linear over the concentration range 1–20 ng/mL; the detection limit for nonylphenol was 0.8 ng/mL.     

Chemoselective cross-metathesis reaction. Application to the synthesis of the C1-C14 fragment of amphidinol 3

[reaction: see text] An efficient synthesis of the C1-C14 fragment of amphidinol 3 is described. The synthesis is based on chemoselective cross-metathesis reactions and enantioselective allyltitanations.     

Solid-supported Hantzsch—Biginelli reaction for syntheses of pyrimidine derivatives

The microwave-assisted dry media technology was utilized for the synthesis of some novel derivatives in the Hantzsch—Biginelli reaction. In this eco-friendly approach, the usage of organic solvents and hazardous reagents resulting in corrossion of materials was minimized, giving high yields of products within a short reaction time.     

Adsorption indicators in the titrations of hexacyanoferrate(II) and oxalate with thorium ions

Alizarin Red S, Pyrocatechol Violet and Xylenol Orange are shown to be effective adsorption indicators for the titrations of hexacyanoferrate(II) and oxalate with Thorium(IV) solution. The action of the indicators can be explained by the theory of surface compound formation.     

Evaluation of some essential and trace elements in diets from 3 nurseries from Juiz de Fora, M.G., Brazil, by neutron activation analysis

A study was made in diets offered to a group of pre-school children,whose mean age was 67 months and remained the whole day in three day carecenters from Juiz de Fora, M.G., Brazil. For sampling, the duplicate portiontechnique was used, and the diets were collected and analyzed separately eachday in the 3 nurseries. Instrumental neutron activation analysis was appliedto the determination of 16 elements. The daily dietary intake values werecompared to the RDA (children 4–6 years old). Based on this reference,Ca, Fe, Se and Zn were found to be deficient, Mg and Mn were comparable tothe RDA and the Cl and Na concentrations were higher compared to their RDA.For the other elements measured, there are no RDA's for children.     

Separation of steroid compounds by overloaded preparative chromatography with precipitation in the fluid phase

In order to gain a commercially acceptable yield compared to the adsorption capacity of the column, a rather large amount of sample is separated with preparative chromatography. During the competitive adsorption of the sample-components, the species adsorbing better can force the rest out of the adsorbent phase. As a consequence, the concentrations of the later components may increase in the fluid phase to a level that those species start to precipitate. A mathematical model which takes the precipitation and dissolution into consideration is presented in this paper. Data calculated by this model are compared to that we obtained by using a previous mathematical model as well as the experimental results gained by a laboratory scale separation of steroid compounds on an organic polymer adsorbent. The equilibrium adsorption-desorption and equilibrium precipitation-dissolution is the first approximation of the complicated process mentioned above. In our next publication we are to extend the model with kinetic terms belonging to adsorption-desorption and precipitation-dissolution process respectively.     

Thio-sugars. IV. Synthesis of carbohydrate 1,3-glycol (six-membered) thionocarbonates and their attempted O-S rearrangement

Four six-membered cyclic thionocarbonates (two sec-sec and two prim-sec) were prepared and their radical-promoted O-S rearrangement reaction was examined. The results revealed that the reaction in six-membered rings is difficult compared with the simple rearrangement in five-membered rings. In the course of syntheses of the substrates, interesting acyl migration during the stannylation process occurred.     

Triterpenoids from Abies species

From an acid fraction of an ethereal extract of Siberian fir needles two new stereoisomeric acids, the molecules of which have a modified lanostane carbon skeleton, have been isolated in the form of methyl esters. The structures of the molecules of these substances have been established by the use of¹³C and¹H NMR,¹H-¹H and¹³C-¹H two-dimensional NMR spectra, circular dichroism, and chemical transformations as (24Z)- and (24E)-8(14 13)-abeo-17,13-friedo-lanosta-8,14(30),24-triene-3,23-dion-26-oic acids.Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR, Novosibirsk. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 511–517, July–August, 1991.