Template effects in the formation of [2]pseudo-rotaxanes containing diazapyrenium units

The template effects exerted by guests 14 and 15 in the ring closure reaction of 3 have been quantitatively evaluated. The rate largely increases in the presence of the two templates. The results are compared with those relative to the ring closure reaction of 1 yielding cyclobis(paraquat-p-phenylene), 2. The comparison indicates that the formation of tetracationic aromatic cycles templated by aromatic donors benefits from the use of extended pi surfaces both in the acceptor and in the donor components.     

Equilibrium dynamics of an associating polymer melt in narrow slits by computer simulation

Molecular dynamics simulations have been used to study the dynamics of a coarse-grained model of a melt of polymer chains with associating terminal groups, confined in a narrow slit by two layers of Lennard-Jones sites. Simulations were carried out as a function of wall separation and attracting strength. We found that confinement has an important effect on the overall dynamics of the system. Strongly attracting walls can significantly modify the dynamics of the melt, giving an aggregation structure with extremely long relaxation times. A noticeable degree of anisotropy was found for the dynamics of both the individual chains and the aggregates formed by the associating terminal groups.     

X-ray and mössbauer studies of tricyclohexyltin(IV) halides. The crystal structures of (cyclo-C6H11)3SnX (X = F,Br and I)

The structures of tricyclohexyltin fluoride (I), bromide (II) and iodide (III) have been determined by X-ray analysis. Compound I crystallizes in the space group P2₁/m with a = 10.422(6), b = 17.238(9), c = 5.769(3) Å, β = 104.6(1)° and Z = 2. Compounds II and III crystallize in the space group Pcmn with a = 10.427(6), b = 16.914(9), c = 11.366(6) Å, Z = 4; and a = 10.400(6), b = 16.900(10), c = 11.400(4) Å, Z = 4, respectively. All three structures consist of discrete tetrahedral (cyclo-C₆H₁₁)₃SnX units.The temperature dependence of the Mössbauer resonance areas has been examined in order to obtain information about the relationship between chemical structure and lattice dynamics.     

NMR J-based analysis of nitrogen-containing moieties and application to dysithiazolamide, a new polychlorinated dipeptide from Dysidea sp.

The methodology of J-based analysis applied to 1,3-methylcarboamido systems allowed us to deduce the relative configurations of the two leucine-like fragments of a new tetrachloro amino acid derivative dysithiazolamide, which was isolated from an unidentified sponge of the genus Dysidea. Furthermore, the absolute configuration was also proposed by comparison with analogous systems.     

High-performance liquid chromatography with post-column derivatisation and fluorescence detection for sensitive determination of aflatoxin M1 in milk and cheese

A new HPLC method with fluorescence detection using pyridinium hydrobromide perbromide as a post-column derivatising agent has been developed to determine aflatoxin M1 in milk and cheese. The detection limits were 1 ng/kg for milk and 5 ng/kg for cheese. The calibration curve was linear from 0.001 to 0.1 ng injected. The method includes a preliminary C18-SPE clean-up and the average recoveries of Aflatoxin M1 from milk and cheese, spiked at levels of 25-75 ng/kg and 100-300 ng/kg, respectively, were 90 and 76%; the precision (RSDr) ranged from 1.7 to 2.6% for milk and from 3.5 to 6.5% for cheese. The method is rapid, easily automatable and therefore useful for accurate and precise screening of aflatoxin M1 in milk and cheese.     

Stemmosides C and D, two novel unusual pregnane glycosides from Solenostemma argel: structural elucidation and configurational study by a combined NMR-quantum mechanical strategy

Stemmosides C and D, two novel pregnane glycosides characterized by an unusual C-17 side chain were isolated from the pericarps of Solenostemma argel. In addition, stemmoside D displays an uncommon 14β proton configuration, apparently being the first pregnane isolated from plants known to have a 15 keto, cis CD ring junction. Their structures have been established by ESIMS and NMR experiments. The relative configuration of the molecules was determined using a strategy based on the simulation of ¹H, ¹³C, and J coupling NMR parameters. DFT calculations of ¹H and ¹³C chemical shifts, and of the ¹H homonuclear spin–spin coupling constants were performed with the mPW1PW91 functional using the 6-31G(d,p) basis set on the fully optimized geometries of all the possible stereoisomers.     

Competitive Gold‐Promoted Meyer–Schuster and oxy‐Cope Rearrangements of 3‐Acyloxy‐1,5‐enynes: Selective Catalysis for the Synthesis of (+)‐(S)‐γ‐Ionone and (−)‐(2S,6 R)‐cis‐γ‐Irone

We report a simple, highly stereoselective synthesis of (+)‐(S)‐γ‐ionone and (‐)‐(2S,6R)‐cis‐γ‐irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)Au^I]‐catalyzed Meyer–Schuster‐like rearrangement. This required a careful investigation of the mechanism of the gold‐catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer–Schuster reaction may compete with the oxy‐Cope rearrangement. Gold‐based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF₆ in 100:1 butan‐2‐one/H₂O, proved to efficiently promote the Meyer–Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}₂(μ‐OH)][BF₄] in anhydrous dichloromethane selectively promoted the oxy‐Cope rearrangement of propargylic alcohols.     

Effect of the π Bridge and Acceptor on Intramolecular Charge Transfer in Push–Pull Cationic Chromophores: An Ultrafast Spectroscopic and TD‐DFT Computational Study

Three (donor–π–acceptor)⁺ systems with a methyl pyridinium or quinolinium as the electron‐deficient group, a dimethyl amino as the electron‐donor group, and an ethylene or butadiene group as the spacer have been investigated in a joint spectroscopic and TD‐DFT computational study. A negative solvatochromism has been revealed in the absorption spectra, which implies a solution color change, and interpreted by considering the variation in the permanent dipole moment modulus and orientation upon photoexcitation. The fluorescence efficiency decreases upon increasing solvent polarity, in agreement with the excited‐state optimized geometries (planar in low‐polarity media and twisted in high‐polarity media). Femtosecond transient absorption has revealed the occurrence of a fast photoinduced intramolecular charge transfer (ICT) and the molecular factors that determine an efficient ICT. Considering the crucial role of the ICT in tuning the nonlinear optical (NLO) properties, these compounds can be considered promising NLO materials.     

Pressure calculation in hybrid particle-field simulations

In the framework of a recently developed scheme for a hybrid particle-field simulation techniques where self-consistent field (SCF) theory and particle models (molecular dynamics) are combined [J. Chem. Phys. 130, 214106 (2009)], we developed a general formulation for the calculation of instantaneous pressure and stress tensor. The expressions have been derived from statistical mechanical definition of the pressure starting from the expression for the free energy functional in the SCF theory. An implementation of the derived formulation suitable for hybrid particle-field molecular dynamics-self-consistent field simulations is described. A series of test simulations on model systems are reported comparing the calculated pressure with those obtained from standard molecular dynamics simulations based on pair potentials.     

TiO2-based photocatalysts impregnated with metallo-porphyrins employed for degradation of 4-nitrophenol in aqueous solutions: role of metal and macrocycle

Photodegradation of organic compounds in water solutions by means of economically advantageous and environment-friendly processes is a topic of growing interest. In recent years a great attention has been devoted to TiO₂-based photocatalysts for the oxidative degradation of various organic pollutants. In this context, we have prepared new photo-catalytic polycrystalline TiO₂ systems impregnated with sensitizers, i.e., copper, iron or manganese porphyrins, and investigated their photoactivity for 4-nitrophenol oxidation compared with that of bare TiO₂. A significant improvement of the photoreactivity was observed in the case of TiO₂ impregnated with copper porphyrin, while only a slight beneficial effect was observed in the case of iron porphyrin. In contrast, the presence of manganese porphyrin appeared to be detrimental.