Synthesis of reversible cyclic peptides

A novel approach for the synthesis of cyclic peptides that can exist in either linear or cyclized conformations is described. Synthesis of the peptides was achieved via a modified solid phase methodology. The reversible linear/cyclized (i.e., open/closed) states are controlled via the reduction/oxidation of a disulfide bond incorporated into the backbone of the peptide chain.     

A catalytic antibody programmed for torsional activation of amide bond hydrolysis

Amidase antibody 312d6, obtained against the sulfonamide hapten 4 a that mimics the transition state for hydrolysis of a distorted amide, accelerates the hydrolysis of the corresponding amides 1 a-3 a by a factor of 10(3) at pH 8. The mechanisms of both the uncatalyzed and antibody-catalyzed reactions were studied. Between pH 8 and 12 the uncatalyzed hydrolysis of N-toluoylindoles 1 a and 3 a shows a simple first-order dependence on [OH(-)], while hydrolysis of 3 a is zeroth-order in [OH(-)] below pH 8. The pH profile for hydrolysis of the corresponding tryptophan amide 2 a is more complex due to the dissociation of the zwitterion into an anion with pK(a) 9.74; hydrolysis of the zwitterionic and the anionic form of 2 a both show simple first-order dependence on [OH(-)]. Absence of (18)O exchange between H(2) (18)O/(18)OH(-) and the substrate, a normal SKIE for both 1 a (k(H)/k(D)=1.12) and 3 a (k(H)/k(D)=1.24) and the value of the Hammett constant rho for hydrolysis of p-substituted amides 3 a-e are consistent with an ester-like mechanism in which formation of the tetrahedral intermediate is rate-determining and the amine departs as anion. The 312d6-catalyzed hydrolysis of 3 a was studied between pH 7.5 and 9, and its independence of pH in this range indicates that water is the reacting nucleophile. Hydrolysis of 3 a is only partially inhibited by the sulfonamide hapten, and this indicates that non-specific catalysis by the protein accompanies the specific process. Only the nonspecific process is observed in the hydrolysis of amides 3 with para substituents other than methyl. Binding studies on the corresponding series of p-substituted sulfonamides 5 a-e confirm the high specificity of antibody 312d6 for p-methyl substituted substrates.     

Three-dimensional low symmetry mesoporous silica structures templated from tetra-headgroup rigid bolaform quaternary ammonium surfactant

Two kinds of highly ordered mesoporous silica materials (FDU-11, FDU-13) with novel three-dimensional (3-D) tetragonal and orthorhombic structures were synthesized by using tetra-headgroup rigid bolaform quaternary ammonium surfactant [(CH(3))(3)NCH(2)CH(2)CH(2)N(CH(3))(2)CH(2)(CH(2))(11)OC(6)H(4)C(6)H(4)O(CH(2))(11)CH(2)N(CH(3))(2)CH(2)CH(2)CH(2)N(CH(3))(3).4Br] (C(3-12-12)(-)(3)) as a template under alkaline conditions. High-resolution transmission electron microscopy (HRTEM), small-angle X-ray scattering (SAXS), and X-ray diffraction (XRD) show that mesoporous silica FDU-11 has primitive tetragonal P4/mmm structure with cell parameters a = b = 8.46 nm, c = 5.22 nm, and c/a ratio = 0.617. N(2) sorption isotherms show that calcined FDU-11 has a high BET surface area of approximately 1490 m(2)/g, a uniform pore size of approximately 2.72 nm, and a pore volume of approximately 1.88 cm(3)/g. Mesoporous silica FDU-13 has primitive orthorhombic Pmmm structure. The cell parameters are a = 9.81, b = 5.67, and c = 3.66 nm. N(2) sorption isotherms show that calcined FDU-13 has a high BET surface area of 1210 m(2)/g, a uniform mesopore size of approximately 1.76 nm, and a large pore volume of approximately 1.83 cm(3)/g. Such low symmetries for 3-D mesostructures (tetragonal and orthorhombic system) have not been observed before even in amphiphilic liquid crystals, which maybe resulted from an oblate aggregation of the bolaform surfactant and its strong electrostatic interaction with inorganic precursor. A probable mechanism has been proposed for the formation of such a 3-D low symmetrical mesostructure. These results will further extend the synthesis of mesoporous materials and may open up new opportunities for their new applications in catalysis, separation, and nanoscience.     

Cobalt(III) complexes of formyl- and acetylpyrazine N(4)-substituted thiosemicarbazones

Cobalt(III) complexes of acetyl- and formylpyrazine N(4)-substituted thiosemicarbazones have been synthesized and characterized by spectral and physical techniques. The crystal structure of the bis{formylpyrazine N(4)-methylthiosemicarbazone}cobalt(III) complex shows the two ligands coordinated in a mer-configuration, and the orientation of the thiosemicarbazone moiety's N(4)-methyl is Z with respect to the thiolato sulfur in both ligands. Included is the crystal structure of the bis- {2-acetylpyridineN(4)-propylthiosemicarbazone}cobalt(III) complex in which the two thiosemicarbazone ligands are also in the mer-configuration, but one ligand has the propyl group oriented Z with respect to the thiolato sulfur and the other E. Both complexes' bond lengths and bond angles are compared with other cobalt(III) thiosemicarbazone complexes.     

New versatile Pd-catalyzed alkylation of indoles via nucleophilic allylic substitution: controlling the regioselectivity

[reaction: see text] A systematic study addressed toward the optimization of the Pd-catalyzed alkylation of indoles by allylic carbonates is presented. The protocol uses a catalytic amount of [PdCl(pi-allyl)](2)/phosphine as a promoting agent, providing allylindoles in excellent yields. The regioselectivity of the reaction can be controlled by a proper choice of the base and the reaction media. The method proved to be effective also for intramolecular allylic alkylations of indolyl carbonates, providing a flexible route to fused indole alkaloids.     

Structural and Coordinative Variability in Zinc(II), Cadmium(II), and Mercury(II) Complexes of 2‐Pyridineformamide 3‐Hexamethyleneiminylthiosemicarbazone

Sodium in dry methanol reduces 2‐cyanopyridine in the presence of 3‐hexamethyleneiminylthiosemicarbazide and produces 2‐pyridineformamide 3‐hexamethyleneiminylthiosemicarbazone, HAmhexim ( 1 ). Complexes with zinc(II ), cadmium(II ) and mercury(II ) have been prepared and characterized by spectroscopic techniques. In addition, the crystal structures of HAmhexim ( 1 ), [Zn(Amhexim)(OAc)]₂μ·μDMSO ( 2 ), [Cd(HAmhexim)Cl₂]μ·μDMSO ( 7 ), [Cd(Amhexim)₂] ( 8 ), [Cd(HAmhexim)Br₂]μ·μDMSO ( 9 ), [Cd(HAmhexim)I₂]μ·μEtOH ( 10 ), [Hg(HAmhexim)Cl₂]μ·μDMSO ( 11 ), [Hg(Amhexim)Br]₂ ( 13 ), [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O ( 14 ) and [Hg(Amhexim)I]₂ ( 15 ) have been determined. Coordination of the anionic and neutral thiosemicarbazone ligand occurs through the pyridine nitrogen atom, imine nitrogen atom, and thiolato or thione sulfur atom. In [Zn(Amhexim)(OAc)]₂ one of the bridging acetato ligands has monodentate coordination and the other bridges in a bidentate manner. [Cd(Amhexim)₂] is a 6‐coordinate species while the other cadmium complexes are 5‐coordinate. In [Hg(Amhexim)Br]₂ and [Hg(Amhexim)I]₂ the thiolato sulfur atoms act as bridges between the Hg atoms to form dimeric compounds and [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O is a trinuclear complex with three different centers — two metallic centers have a 5‐coordination and the another one has 4‐coordination. In addition, [Hg(HAmhexim)Cl₂]μ·μDMSO and [Hg₃(HAmhexim)(Amhexim)Br₅]μ·μH₂O shown a supramolecular one‐dimensional hydrogen‐bonded self‐assembling.     

Limiting equations in asymptotic stability problems for nonautonomous differential equations

Summary By limiting equations, we prove some asymptotic stability theorems for the origin ofR ⁿ with respect to the solutions of a differential equation , also when the functionf is not defined forx=0. Further we examine similar problems concerning the asymptotic stability of a setM ofR ⁿ that can be unbounded.

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Riassunto Mediante le equazioni limiti, si dimostrano alcuni teoremi di stabilità asintotica per l'origine diR ⁿ rispetto alle soluzioni di un'equazione differenziale , anche quando la funzionef non è definita perx=0. Vengono inoltre esaminati analoghi problemi relativi alla stabilità asintotica di un insiemeM diR ⁿ anche non limitato.

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Work performed under the auspices of the Italian Council of Research (G.N.F.M. del C.N.R.).     

Derivatives of rhodanine as spectrophotometric analytical reagents : I. Condensation at C-5 with aromatic pyridine and nonpyridine aldehydes

The synthesis, characteristics, properties, and reactions with metallic ions of five aromatic (three nonpyridine and two pyridine) derivatives of rhodanine have been studied. Nonpyridine derivatives exhibit one pK value in aqueous solution and two pyridine reagents, and with Pd(II), Au(III), Hg(II), and Cu(I) and (II) form stable complexes which show an absorption band, at the visible zone of the spectrum, with molar absorptivities adequate for spectrophotometric measurements. Finally, suggestions have been made about the group responsibile for the reactionability.     

Cationic benzyl zirconium heteroscorpionates: synthesis and characterization of a novel ethylene polymerisation catalyst showing an unusual temperature dependent polymerisation mechanism

The reaction of (bpzmp)Zr(CH2Ph)3 with B(C6F5)3 produces the active ethylene polymerisation catalyst [(bpzmp)Zr(CH2Ph)2]+[PhCH2B(C6F5)3]- which showed a temperature dependent polymerisation mechanism identified by variable temperature 1H NMR analysis of the catalyst solution.     

Semicarbazones and thiosemicarbazones,XIII: Study of the hydrolysis of coordinated thiosemicarbazones

Summary The hydrolysis of coordinated thiosemicarbazones was studied. It was found that the nickel(II) ion promotes the reaction. Steric and electronic influences were found. The hydrolysis ofATSC in the trigonal bipyramid compounds [M(ATSC)₂Cl]Cl [M=Fe(II), Co(II), Ni(II)], is higher with the Ni(II) complex, the compound with the shorterM-N distance.

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Semicarbazone und Thiosemicarbazone, 13. Mitt.: Untersuchungen zur Hydrolyse koordinierter Thiosemicarbazone

Zusammenfassung Bei der Hydrolyse von koordinierten Thiosemicarbazonen wurde festgestellet, daß das Nickel(II)-Ion die Reaktion begünstigt. Es wurden sterische und elektronische Einflüsse gefunden. Die Hydrolysengeschwindigkeit desATSC im trigonal bipyramidalen Komplex [M(ATSC)₂Cl]Cl [M=Fe(II), Co(II), Ni(II)] ist höher mit dem Ni(II)-Komplex, der Verbindung mit der kürzerenM-N-Distanz.