Toward block copolymers from nonliving isospecific single‐site catalytic systems

Ethene/1‐olefin blocky copolymers were obtained through nonliving insertion copolymerizations promoted by an isospecific single site catalyst. Propene or 4‐methyl‐1‐pentene were copolymerized with ethene with metallocenes endowed with different stereospecificity in propene polymerization: (i) aspecific “constrained geometry” half‐sandwich complex, {η¹:η⁵‐([tert‐butyl‐amido)dimethylsilyl](2,3,4,5‐tetramethyl‐1‐cyclopentadienyl)}titanium dichloride [Me₂Si(Me₄Cp)(N‐^tBu)TiCl₂] ( CG ), (ii) moderately isospecific rac‐ethylenebis(indenyl)zirconium dichloride [rac‐(EBI)ZrCl₂] ( EBI ), (iii) slightly more isospecific hydrogenated homologue, rac‐ethylenebis(tetrahydroindenyl)zirconium dichloride [rac‐(EBTHI)ZrCl₂] ( EBTHI ), (iv) highly iso‐specific rac‐[methylenebis(3‐tert‐butyl‐1‐indenyl)]zirconium dichloride [rac‐H₂C‐(3‐^tBuInd)₂ZrCl₂] ( TBI ), (v) most isospecific rac‐[isopropylidene‐bis(3‐tert‐butyl‐cyclopentadienyl)]zirconium dichloride [rac‐Me₂C‐(3‐^tBuCp)₂ZrCl₂] ( TBC ). Copolymerizations were described by a 2^nd order Markovian copolymerization model and data are proposed to correlate the formation of 1‐olefin sequences with catalytic site isospecificity, made by the cooperation of organometallic complex and growing chain. Blocky copolymers were prepared over wide ranges of compositions: with any of the isospecific metallocenes when 4‐methyl‐1‐pentene was the 1‐olefin and only with the highly isospecific ones ( TBI , TBC ) when propene was the comonomer. A penultimate unit effect was observed with TBI as the metallocene, whereas a 1^st order Markov model described the ethene/propene copolymerization from TBC . A moderately isospecific metallocene, such as EBI , is shown to be able to prepare blocky ethene copolymers with 4‐methyl‐1‐pentene. These results pave the way for the synthesis of new ethene based materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2063–2075, 2010     

Enantioselective synthesis of 1-(R)-hydroxypolygodial and its 9α epimer, 1-(R)-hydroxyisotadeonal

The enantioselective synthesis of 1-(R)-hydroxypolygodial and its epimer at C-9 is described. α-Ionone was the starting material. Key steps of these syntheses included a Corey-Bakshi-Shibata oxazaborolidine-mediated reduction and a stereoselective Diels-Alder reaction. No vanilloid activity was detected for both compounds in assays on VR1 vanilloid receptor in HEK cells transfected with the human VR1.     

Near‐Infrared Emission Quantum Yield of Soluble Short Single‐Walled Carbon Nanotubes

Soluble short single‐walled carbon nanotubes in aerated D₂O emit in the near‐infrared (NIR) region (see picture) with a quantum yield of (3.9±0.5) ×10^?3 and a half‐life of 7.65 μs. This emission is quenched by electron‐ acceptor molecules.

     

A note on the numerical resolution of Heston PDEs

Ricerche di Matematica - In this paper we aim to compare a popular numerical method with a new, recently proposed meshless approach for Heston PDE resolution. In finance, most famous models can be...     

An existence result of a quasi-variational inequality associated to an equilibrium problem

In this paper we consider a Walrasian pure exchange economy with utility function which is a particular case of a general economic equilibrium problem, without production. We assume that each agent is endowed with at least of a commodity, his preferences are expressed by an utility function and it prevails a competitive behaviour: each agent regards the prices payed and received as independent of his own choices. The Walrasian equilibrium can be characterized as a solution to a quasi-variational inequality. By using this variational approach, our goal is to prove an existence result of equilibrium solutions.     

Preparation,proton and carbon-13 structure determination,and fungicidal activity of chlorinated 1-arylamino-1H-pyrrole-2,5-diones

1-(2′,4′-dichloro)phenylamino-1H-pyrrole-2,5-dione and 1-(2′,4′,6′-trichloro)phenylamino-1H-pyrrole-2,5-dione were prepared via direct chlorination of 2-phenyl-3-oxo-6-hydroxy-2H-pyridazine. Both pmr and mass spectroscopy clearly showed that dichloro substitution occurred in the aromatic moiety and not in the vinylic region of the molecule. The former method showed that pyridiazine- to pyrrole-ring isomerization had occurred already at the level of dichlorination. The identical 2′,4′-dichlorophenyl and 2′,4′,6′-trichlorophenylpyr-rolediones were also prepared by reaction of maleic anhydride with the appropriate arylhydrazine. Similar 2′,4-dichlorophenyl and 2′,4′,6′-trichlorophenyl analogues were prepared using dichloromaleic anhydride. Cmr spectroscopic techniques were used for pyridazine-/pyrrole-ring stereochemical assignment of products derived from dichloromaleic anhydride. 1-(2′,4′-dichloro)phenylamino-1H-pyrrole-2,5-dione and the trichloro-phenyl analogue were shown to exhibit fungicidal activity in both in-vivo and in-vitro assays.     

Enantioselective synthesis of 1(R)-hydroxypolygodial

Enantioselective preparation of 1(R)-hydroxypolygodial (5) has been achieved starting from α-ionone through a synthetic strategy involving a Corey-Bakshi-Shibata oxazaborolidine-mediated reduction and a stereoselective Diels-Alder reaction as key steps.     

Alkene-directed, nickel-catalyzed alkyne coupling reactions

In alkene-directed, nickel-catalyzed coupling reactions of 1,3-enynes with aldehydes and epoxides, the conjugated alkene dramatically enhances reactivity and uniformly directs regioselectivity, independent of the nature of the other alkyne substituent (aryl, alkyl (1 degrees , 2 degrees , 3 degrees )) or the degree of alkene substitution (mono-, di-, tri-, and tetrasubstituted). These observations are best explained by a temporary interaction between the alkene and the transition metal center during the regioselectivity-determining step. The highly substituted 1,3-diene products are useful in organic synthesis and, in conjunction with a Rh-catalyzed, site-selective hydrogenation, afford allylic and homoallylic alcohols that previously could not be prepared in high regioselectivity (or at all) with related Ni-catalyzed alkyne coupling reactions.     

Metal content in river suspended particulate matter: data on Po River

The present study summarizes the last ten years of literature on heavy metal distribution in Suspended Particulate Matter (SPM) and dissolved phase in the Po River (Italy). The work compares different methodologies employed to collect, concentrate and fractionate the samples. The importance of metal speciation as a function of particle size is underlined and two approaches to metal speciation in the colloidal fraction of Po River SPM are presented: Sedimentation Field-Flow Fractionation (SdFFF) and pH-dependent extractions. Finally, emphasis is placed on the need for comparison with a reference "natural background level" of the metal load in Po River particulate matter in order to determine the real human contribution to river pollution. The high values of some trace transition elements, such as Cr and Ni, have been compared with clay sediments around Ferrara and with bricks in historic buildings. The highly comparable natural concentration of these metals in Po fine sedimentary rocks and in historic brick buildings of Ferrara (XII-XVI centuries) can provide information on natural geochemical anomalies.