Alkylation ofβ-diketones of the hexahydroindan series and their enamines

Conclusions The reactions of hexahydro-1,3-indandlone with ammonia and some amines were studied, and the structures of the products formed were proved. In the alkylation of-diketones of the hexahydroindan series and their enamines under the usual conditions C-alkylation products are not formed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1214–1218, July, 1966.     

Formation of adenine-N3/guanine-N7 cross-link in the reaction of trans-oriented platinum substrates with dinucleotides

The reactions of the anticancer complex trans-[PtCl2{(E)-HN=C(OMe)Me}2] (trans-EE) with a series of ribo and deoxyribodinucleotides have been studied by HPLC and 2D [1H, 15N] HMQC NMR spectroscopy and compared with those of the inactive trans isomer of cisplatin, trans-[PtCl2(NH3)2] (trans-DDP). Reactions of trans-EE with r(ApG) and d(ApG) take place through solvolysis of the starting substrate and subsequent formation of trans G-N7/monochloro and G-N7/monoaqua adducts. Slowly, the monofunctional adducts evolve to a bifunctional adduct forming an unprecedented and unexpected A-N3/G-N7 platinum cross-link spanning two trans positions. For stereochemical reasons, trans platinum complexes cannot form N7/N7 cross-links between adjacent purines in di- or polynucleotides. For the reverse sequence r(GpA), no chelate structure was formed even after a two-week reaction. The reaction of trans-DDP with r(ApG) produces many more products than the analogous reaction with trans-EE. One of these products was identified as the A-N3/G-N7 trans-chelate.     

Thiazolium-catalyzed intermolecular Stetter reaction of linear and cyclic alkyl α-diketones

An efficient method for the N-heterocyclic carbene (NHC)-catalyzed conjugate addition of acetyl anions to various α,β-unsaturated acceptors (Stetter reaction) has been optimized by using 2,3-butandione (biacetyl) as an alternative surrogate of acetaldehyde. The disclosed procedure proved to be compatible with microwave dielectric heating for reaction time reduction and with the use of different linear α-diketones as acyl anion donors (e.g. 3,4-hexanedione for propionyl anion additions). Moreover, the unprecedented umpolung reactivity of cyclic α-diketones in the atom economic nucleophilic acylation of chalcones is herein presented. Mechanistic aspects of the thiazolium-based catalysis involving linear and cyclic α-diketone substrates are also discussed.     

Thermodynamic Formalism for Contracting Lorenz Flows

We study the expansion properties of the contracting Lorenz flow introduced by Rovella via thermodynamic formalism. Specifically, we prove the existence of an equilibrium state for the natural potential [^( j)]_t(x,y,z):=-tlogJ_(x,y,z)^cu\hat{ \varphi }_{t}(x,y,z):=-t\log J_{(x,y,z)}^{cu} for the contracting Lorenz flow and for t in an interval containing [0,1]. We also analyse the Lyapunov spectrum of the flow in terms of the pressure.     

Synthesis and optical characterization of submicrometer gold nanotubes grown on goethite rods

Goethite (FeOOH) rods were used as templates for growing gold nanotubes with a length of a few hundred nanometers and an aspect ratio between 3 and 4. Successful uniform growth required surface modification, followed by the attachment of small Au seeds and one-step seeded growth using formaldehyde as a reducing agent, as previously reported for the growth of Au shells on silica spheres and hematite spindles. The thickness and surface roughness of the obtained shells could be adjusted by simply varying the concentration ratio between seeds (modified goethite rods) and growth reagents (HAuCl 4 and formaldehyde). The morphology of the synthesized gold nanotubes was thoroughly characterized by TEM, SEM, and AFM/MFM. The resulting gold nanotubes display well-defined plasmon resonances, with a strong longitudinal mode centered around ca. 1400 nm and a broad band in the visible resulting from the overlap of a transverse mode and a multipolar mode, as was found from theoretical modeling using the boundary element method, which provides reasonable agreement with the experimental results.     

Conformer distribution in (cis-1,4-DACH)bis(guanosine-5'-phosphate)platinum(II) adducts: a reliable model for DNA adducts of antitumoral cisplatin

In [PtCl2(cis-1,4-DACH)] (DACH = diaminocyclohexane), the N-Pt-N bite angle (> or =97 degrees , as determined by X-ray diffraction analysis) is much larger than those found in other Pt complexes with bidentate diamines or in cisplatin (approximately 91 degrees ). Hence, the possibility exists that in (cis-1,4-DACH)PtG 2 adducts, rotation of the G's around the Pt-N7 bonds is slowed enough to allow observation of different conformers. In accord with this prevision, decreasing the temperature to 238 K enabled us to observe different conformers of (cis-1,4-DACH)Pt(5'-GMP) 2 (GMP = guanosine monophosphate). This observation is the first case in which such conformers for a platinum derivative with primary diamines and untethered guanines have been resolved and represents the closest model to clinically effective cisplatin obtained to date. We also found that the presence of the 1,4-DACH ligand increased the intensity of the circular dichroism signal stemming from the dominance of an HT conformer (DeltaHT in the adduct with 3'-GMPs and LambdaHT in the adduct with 5'-GMPs).