Miniature electrophoresis for speed and productivity

Attempts to miniaturize electrophoresis (EP) to save time or enhance productivity and efficiency remains a challenge for science and industry. Other advantages of miniaturization include: increased sensitivity, saving of reagents, greater yield of data, and enabling studies where only small samples are available. Since electrophoresis that takes hours may be reduced to a matter of minutes, the limitations of miniaturization in clinical, industrial, and research applications are evaluated. Clinical electrophoresis (EP) on cellulose acetate media can be performed in 3.5 min instead of 20–45 min and on SDS polyacrylamide gels in 15–30 min compared with conventional 3–8 h.     

Syntheses and structures of structurally diverse potassium beta-diketiminates derived from the ligand [(N(SiMe3)C(Ph))2CH

The compounds [K((mu-N(SiMe3)C(Ph))2CH)(thf)2]infinity 1, [K(mu-N(SiMe3)C(Ph)C(H)C(Ph)NH)L]2 [L = (thf)2 2, tmen 3], [K(mu-NSi(Me)2C(Ph)C(H)C(Ph)N)(thf)3]2 4 and [K(N(H)C(Ph))2CH](thf)0.5 5 have been prepared from K[(N(SiMe3)C(Ph))2CH] and the X-ray structures of 1-4 are reported.     

Azetidinyl ketones. Synthesis of 1-Alkyl-2,4-diphenyl-3-benzoylazetidines

α-(α'-Bromobenzyl)chalcone ( 3 ) reacts with primary amines (t-butyl, isopropyl,cyclohexyl) to give α-(α'-alkylaminobenzyl)chalcones ( 4, 5 and 6 ). When these allylic amines are treated with hydrogen bromide followed by reaction with base, they produce l-alkyl-2,4-diphenyl-3-benzoyl-azetidines ( 7,8 and 9 ). These azetidines were readily converted to their 3-deuterio derivatives ( 10 , 11 and 12 ) by treatment with sodium methoxide in deuteriomethanol. The configurations were assigned primarily by pmr spectra and mass spectra in reference to analogous compounds.     

Equilibrium interaction of solid surfaces across a polymer melt

Forces across polymer melts are poorly understood despite their importance for adhesion and fabricating composite materials. Using an atomic force microscope (AFM), this interaction was measured for poly(dimethyl siloxane) (PDMS). The structure of the polymer at the surface changed during the first approximately 10 h. Afterward, short-range attractive forces were observed with short-chain PDMS (M(w) = 4200 g/mol). Using PDMS with a molecular weight (M(w) = 18 000 g/mol) above the entanglement limit, we measured a monotonically decaying repulsive force, which indicates that a quasi-immobilized layer had formed at the solid surface. Due to the small radius of curvature of the tip, forces could be measured in equilibrium.     

Two unusual, competitive mechanisms for (2-ethynylphenyl)triazene cyclization: pseudocoarctate versus pericyclic reactivity

The cyclization of (2-ethynylphenyl)triazenes in ODCB at 200 degrees C gives exclusively cinnolines, whereas addition of CuCl to 1,2-dichloroethane solutions of the triazenes at 50 degrees C results in the sole formation of isoindazoles. DFT calculations and deuterium labeling studies suggest the intermediacy of a 3-dehydrocinnolinium ion, produced through a pericyclic transition state. Calculations and trapping studies strongly implicate a carbene intermediate in isoindazole formation, which proceeds through a pseudocoarctate transition state.     

Enantiomerentrennung und chiroptische Eigenschaften eines 2,3-Dihydrobilatriens-abc

The enantiomers of the 2,3-dihydrobilatriene-abc1 have been separated by recycling chromatography on triacetylcellulose. Comparison of their chiroptical properties with those of amino acid substituted analogues, like3, reveals the chirality of center 3 to be of minor influence on the values. Stabilization of a definite helical conformation of these pigments seems to depend on this influence together with an appropriate dipole-dipole interaction.

     

Heterogeneous reactions : VI. Reactions of trimethylchlorosilane,dimethyldichlorosilane and chloromethyldimethylchlorosilane with potassium t-butoxide and sodium methoxide

The heterogeneous gas-solid reaction of trimethylchlorosilane and an equal molar mixture of potassium t-butoxide and sodium methoxide gave exclusively trimethyl-t-butoxysilane. A similar reaction utilizing dimethyldichlorosilane as the vapor phase substrate gave predominant incorporation of butoxide. The heterogeneous reaction of chloromethyldimethylchlorosilane with these two bases was extensively studied. The parameters investigated for the latter system include the dependence of the product distribution on temperature, nitrogen flow rate and the relative hydroxide content of the solid alkoxide base. These studies allow the assessment of the relative reactivities of these bases under the conditions of heterogeneous gas/solid reaction. Under these conditions and with partially hydrolyzed bases a substantial amount of displacement of the chloromethyl group from chloromethyldimethylchlorosilane is observed. The role of hydroxide ion in this reaction is discussed. Convenient syntheses of t-butyl methyl ether and dimethylchloromethoxysilane are reported.     

Über einige neue Bispirane

We have obtained four new bispirane systems in which both spiroatoms are vicinal atoms in cyclopropane or cyclobutane rings and in which the heterocyclic component has the basic structure of 1,4-dioxep-2-ene. We have shown that from two possibilities (bispiran, propellan) the general reaction leads only to a bispiran system. To the bispiran2 exhibiting the highest hyperchromism we ascribed the bispirocoplanar conformation (Fig. 1).

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Mit 3 Abbildungen     

A modification of the heteropoly blue method for the microgram determination of arsenic in biological materials

Summary A sensitive method has been developed for analysis of trace amounts of arsenic in biological materials using the heteropoly blue method. The method employs a closed apparatus and a nitrogen atmosphere, and allows the detection of arsenic in ppm concentration using samples of 100 mg.

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Zusammenfassung Eine empfindliche Methode zur Bestimmung von Arsenspuren in biologischem Material im Wege der Molybdänblaumethode wurde ausgearbeitet. Man arbeitet dabei in einer geschlossenen Apparatur in Stickstoffatmosphäre und kann so in 100-mg-Proben Arsenkonzentrationen in der Größenordnung von ppm bestimmen.

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Presented at the 6th Annual Northeast Regional Meeting of the American Chemical Society, Burlington, Vermont, August 19, 1974.