Micellar electrokinetic capillary chromatographic separation and laser-induced fluorescence detection of 2'-deoxynucleoside 5'-monophosphates of normal and modified bases

Micellar electrokinetic chromatography is used to separate dansylated nucleotides, both normal and modified species. The high separation power allows detection of minor components present in less than 1 part per thousand of the major components. Laser-excited fluorescence is used to detect the separated components at the 6 x 10(-18) mol level or 10(-9) M injected material. Combined with high-performance liquid chromatographic enrichment prior to labeling, this technique can be used to assess DNA damage in carcinogenesis studies.     

The structure of malabricol

A single crystal X-ray analysis has confirmed the constitution and established the stereochemistry of the triterpene, malabaricol.     

Polymerization of para-xylylene derivatives (parylene polymerization). I. Deposition kinetics for parylene N and parylene C

Kinetic aspects of parylene N [unsubstituted poly(para-xylylene)] and Parylene C [monochlorosubstituted poly(para-xylylene)] were studied. The conversion of starting material (dimer of either p-xylylene or chloro-para-xylylene) to polymer is quantitative (ca. 100%). Consequently, the total polymer formed in a closed system is directly proportional to the amount of dimer charged. However, the percentage of the total amount of polymer formed which deposits on substrate surfaces, placed in the deposition chamber, as well as the polymer film growth rate are dependent on operational factors such as the temperature of the substrate, sublimation of dimer temperature, flow pattern of the reactive species, etc. Parylene C, being a heavier and more polar molecule, has the tendency to deposit easily in the deposition chamber compared to the deposition of Parylene N. Parylene C also has a higher ceiling temperature for deposition than Parylene N. This situation has been investigated from the viewpoint of excess thermal energy which hinders polymer formation (deposition) due to the exceedingly high entropy change necessary for polymer deposition to occur. The addition of a cool (i.e., room temperature) inert gas was shown to increase the deposition of Parylene N on substrate surfaces placed in the deposition chamber. The deposition increase and acceleration of deposition (film growth) rate were found to be related to the size and molecular weight of the inert gas pressure maintained in the system. The accelerating effect is explained by the increase in third-body collisions to dissipate the excess thermal energy of the reactive species.     

The synthesis of N-substituted ketimines from oxazirdines

N-Unsubstituted diaryl, alkyl aryl and dialkyl ketimines are prepared in good yield at ambient temperature by the reaction of KOBu^t on oxaziridines having an α-hydrogen atom on the N-alkyl substituent; the mechanism and stereochemistry of the reaction are discussed.     

Deoxygenation of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones with Mg-MeOH

The deoxygenation of a variety of sulfoxides, selenoxides, telluroxides, sulfones, selenones and tellurones has been reported with Mg-MeOH at room temperature in nearly quantitative yields. The deoxygenation is proposed to proceed by SET from Mg to the substrate.     

New ruthenium-based protocol for cleavage of terminal olefins to primary alcohols: improved synthesis of a bicyclic nucleoside

A new protocol for the oxidative cleavage of terminal alkenes to give exclusively primary alcohols in high yields is introduced. The protocol is based on RuO4-mediated dihydroxylation, NaIO4-mediated diol cleavage, and NaBH4-mediated reduction, but the introduction of a reducing step before the diol cleavage removes the formation of byproducts and improves the yield significantly. The new protocol has been developed and used for the improved preparation of a [3.2.0]bicycloarabinonucleoside with important potential in antisense and antigene technology.     

Thermal studies of some aryloxides of titanium(IV)

Thermal behaviour of aryloxides of titanium(IV) of composition TiCl_n(OAr)_4?n (wheren=0→3 and OAr=OC₆Bu^t-4, OC₆H₄OMe-4 and OC₆H₂-Bu ₂ ^t -2,6?Me-4) has been studied by DTA and TG analysis. Multiple decomposition steps have been indicated by thermal weight losses which are both exothermic and endothermic as shown by DTA curves. Based upon the total % loss in weight; during entire decomposition titanium dioxide has been found to be the final residue in each case.     

Products active on arthropod-IV Insect juvenile hormone mimics—4: hydrindane analogues of cecropia juvenile hormone

Synthesis of cis-hydrindane analogues (2,3) of Cecropia juvenile hormone-I from common intermediate cis-hydrindane-2, 5-dione is presented. The analogues are only moderately active against Dysdercus cingulatus.     

New organosols of nickel sulfides,palladium sulfides,manganese sulfide,and mixed metal sulfides and their use in preparation of semiconducting polymer-metal sulfide composites

Organosols of NiS, PdS, and MnS in N,N-dimethylformamide were prepared by reaction of the metal acetate with H₂S. Organosols of mixed-metal sulfides (Zn _x Cd_1–x S, Hg _x Cd_1–x S, Hg _x Cu_1–x S, Cd _x Mn_1–x S, Hg _x Mn_1–x S, Hg _x Cd_1–x S, and Mn _x Zn_1–x S) were similarly obtained by reaction of mixtures of the metal salts with H₂S. The organosol of Zn_0.5Cd_0.5S contained particle with two particle size distributions centered at 6.5 nm and 29 nm, as revealed by Ar laser-scattering analysis. The metal sulfides are recovered by addition of Et₂O to the organosols. Zn _x Cd_1–x S thus obtained shows magnetic susceptibility in the range 0.5×10^–6–2.3×10^–6 emug^–1 depending on thex value. Addition of polymers to the organosols affords semiconducting films of metal sulfide-polymer composites.     

Products active on mosquitoes,IV: Synthesis and biological activity of 8-propargyloxy-3,7-dimethyl-2,6-octadienyl/6-octenyl ethers

Summary A series of 8-proparglyoxy-3,7-dimethyl-2,6-octadienyl and 8-propargyloxy-3,7-dimethyl-6-octenyl ethers were prepared from 8-hydroxygeranyl and 8-hydroxycitronellyl ethers, respectively. Almost all compounds showed high toxicity toCulex quinquefaciatus larvae at 1 mgl^–1 dose level.

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Gegen Mücken aktive Produkte, 4. Mitt.: Synthese und biologische Aktivität von 8-Propargyloxy-3,7-dimethyl-2,6-octadienyl/6-octenyl-ethern

Zusammenfassung Eine Reihe von 8-Propargyloxy-3,7-dimethyl-2,6-octadienyl- und 8-propargyloxy-3,7-dimethyl-6-octenyl-ethern wurden aus 8-Hydroxygeranyl- bzw. 8-Hydroxycitronellyl-ethern hergestellt. Fast alle Verbindungen zeigten hoch Toxizität gegenüber Larven vonCulex quinquefaciatus in einer Dosierung von 1 mgl^–1.