Liquid chromatographic isolation of coplanar PCB congeners on an activated carbon stationary phase

A rapid and uncomplicated method for the fractionation of PCBs leading to an isolation of the highly toxic non-ortho substituted PCBs is described. The liquid chromatographic separation was achieved on a stationary phase consisting of activated carbon and Celite 545. Using eluents with different polarity, isolation of the non-ortho substituted PCBs in a single fraction was achieved. The fractions were analysed by GC/MS. The method was tested by the determination of non-ortho substituted PCBs in technical mixtures (Aroclor 1254 and Aroclor 1242). The results were compared with those obtained by using an HPLC fractionation on a porous graphitic carbon column. Finally, the micro-column fractionation was used for the determination of non-ortho substituted PCBs in native soil samples. Received: 5 March 1997 / Revised: 4 June 1997 / Accepted: 6 June 1997     

Efficient Entropy-Driven Inhibition of Dipeptidyl Peptidase III by Hydroxyethylene Transition-State Peptidomimetics

Dipeptidyl peptidase III (DPP3) is a ubiquitously expressed Zn-dependent protease, which plays an important role in regulating endogenous peptide hormones, such as enkephalins or angiotensins. In previous biophysical studies, it could be shown that substrate binding is driven by a large entropic contribution due to the release of water molecules from the closing binding cleft. Here, the design, synthesis and biophysical characterization of peptidomimetic inhibitors is reported, using for the first time an hydroxyethylene transition-state mimetic for a metalloprotease. Efficient routes for the synthesis of both stereoisomers of the pseudopeptide core were developed, which allowed the synthesis of peptidomimetic inhibitors mimicking the VVYPW-motif of tynorphin. The best inhibitors inhibit DPP3 in the low μM range. Biophysical characterization by means of ITC measurement and X-ray crystallography confirm the unusual entropy-driven mode of binding. Stability assays demonstrated the desired stability of these inhibitors, which efficiently inhibited DPP3 in mouse brain homogenate.     

Pore Development during the Carbonization Process of Lignin Microparticles Investigated by Small Angle X-ray Scattering

Application of low-cost carbon black from lignin highly depends on the materials properties, which might by determined by raw material and processing conditions. Four different technical lignins were subjected to thermostabilization followed by stepwise heat treatment up to a temperature of 2000 °C in order to obtain micro-sized carbon particles. The development of the pore structure, graphitization and inner surfaces were investigated by X-ray scattering complemented by scanning electron microscopy and FTIR spectroscopy. Lignosulfonate-based carbons exhibit a complex pore structure with nanopores and mesopores that evolve by heat treatment. Organosolv, kraft and soda lignin-based samples exhibit distinct pores growing steadily with heat treatment temperature. All carbons exhibit increasing pore size of about 0.5–2 nm and increasing inner surface, with a strong increase between 1200 °C and 1600 °C. The chemistry and bonding nature shifts from basic organic material towards pure graphite. The crystallite size was found to increase with the increasing degree of graphitization. Heat treatment of just 1600 °C might be sufficient for many applications, allowing to reduce production energy while maintaining materials properties.     

Synthese und Struktur von γ-Halogenpropyl-octa(silasesquioxanen)

Synthesis and Structures of γ-Halopropyl-octa(silasesquioxanes) As a more rapid and versatile synthetic approach, we have studied the FeCl₃-catalyzed hydrolytic polycondensation of suited trichlorosilanes in a biphasic system which yields e.g. the new octa(silasesquioxane) (BrCH₂CH₂CH₂)₈Si₈O₁₂.     

Functionalization of single-walled carbon nanotubes via the Bingel reaction

Single-walled carbon nanotubes have been cyclopropanated under Bingel reaction conditions, and the functionalized nanotubes have been characterized by atomic force microscopy using "chemical tagging" techniques.     

Unprecedented head-to-head conformers of d(GpG) bound to the antitumor active compound tetrakis (mu-carboxylato)dirhodium(II,II)

The N7/O6 equatorial binding interactions of the antitumor active complex Rh(2)(OAc)(4)(H(2)O)(2) (OAc(-) = CH(3)CO(2)(-)) with the DNA fragment d(GpG) have been unambiguously determined by NMR spectroscopy. Previous X-ray crystallographic determinations of the head-to-head (HH) and head-to-tail (HT) adducts of dirhodium tetraacetate with 9-ethylguanine (9-EtGH) revealed unprecedented bridging N7/O6 guanine nucleobases that span the Rh-Rh bond. The absence of N7 protonation at low pH and the notable increase in the acidity of N1-H (pK(a) approximately 5.7 as compared to 8.5 for N7 only bound platinum adducts), suggested by the pH dependence titrations of the purine H8 (1)H NMR resonances for Rh(2)(OAc)(2)(9-EtG)(2) and Rh(2)(OAc)(2-)[d(GpG)],are consistent with bidentate N7/O6 binding of the guanine nucleobases. The pK(a) values estimated for N1-H (de)protonation, from the pH dependence studies of the C6 and C2 (13)C NMR resonances for the Rh(2)(OAc)(2)(9-EtG)(2) isomers, concur with those derived from the H8 (1)H NMR resonance titrations. Comparison of the (13)C NMR resonances of C6 and C2 for the dirhodium adducts Rh(2)(OAc)(2)(9-EtG)(2) and Rh(2)(OAc)(2)[d(GpG)] with the corresponding resonances of the unbound ligands [at pH 7.0 for 9-EtGH and pH 8.0 for d(GpG)], shows substantial downfield shifts of Deltadelta approximately 11.0 and 6.0 ppm for C6 and C2, respectively; the latter shifts reflect the effect of O6 binding to the dirhodium centers and the ensuing enhancement in the acidity of N1-H. Intense H8/H8 ROE cross-peaks in the 2D ROESY NMR spectrum of Rh(2)(OAc)(2)[d(GpG)] indicate head-to-head arrangement of the guanine bases. The Rh(2)(OAc)(2)[d(GpG)] adduct exhibits two major right-handed conformers, HH1 R and HH2 R, with HH1 R being three times more abundant than the unusual HH2 R. Complete characterization of both adducts revealed repuckering of the 5'-G sugar rings to C3'-endo (N-type), retention of C2'-endo (S-type) conformation for the 3'-G sugar rings, and anti orientation with respect to the glycosyl bonds. The structural features obtained for Rh(2)(OAc)(2))[d(GpG)] by means of NMR spectroscopy are very similar to those for cis-[Pt(NH(3))(2))[d(GpG)]] and corroborate molecular modeling studies.     

Purification of Single-walled Carbon Nanotubes Grown by a Chemical Vapour Deposition (CVD) Method

ＩｎｔｒｏｄｕｃｔｉｏｎＳｉｎｇｌｅ ｗａｌｌｅｄｃａｒｂｏｎｎａｎｏｔｕｂｅｓ(ＳＷＮＴｓ)ｈａｖｅｂｅｅｎｓｙｎｔｈｅｓｉｓｅｄｂｙｕｓｉｎｇｖａｒｉｏｕｓｍｅｔｈｏｄｓ[1— 3] ａｎｄｔｈｅｃｈｅｍｉｃａｌｖａｐｏｕｒｄｅｐｏｓｉｔｉｏｎ (ＣＶＤ )ｍｅｔｈｏｄｈａｓｂｅｅｎｃｏｎｓｉｄｅｒｅｄａｓａ ｐｒｏｍｉｓｉｎｇｍｅｔｈｏｄｔｏ ｐｒｏｄｕｃｅＳＷＮＴｓｏｎａｎｉｎｄｕｓｔｒｉａｌｓｃａｌｅ[3— 5] .Ｈｏｗｅｖｅｒ ,ａｌｌｔｈｅＳＷＮＴ ｐｒｏｄｕｃｔｓｓｙｎｔｈｅｓｉｓｅｄｔｏｄａｔｅｃｏ…     

Anion sensing 'venus flytrap' hosts: a modular approach

A series of podands based on three hydrogen bonding 'arms' have been prepared and their affinities for simple inorganic anions measured.