Polymerization with Fischer-Tropsch olefins – a new challenge in polymer science

Co- and ter-polymerization of ethylene with Fischer-Tropsch derived olefins having odd carbon number and branched olefins are investigated. A method of preparation of a robust, high productivity Ziegler-Natta catalyst suitable for ethylene co-polymerization with Fischer Tropsch olefin is reviewed. In supporting titanium tetrachloride, an attempt was made to control the titanium oxidation state. The resulting experimental data were fitted to a sub-sites model that associates titanium oxidation state with catalyst activity.     

Positive Cooperativity Induced by Interstrand Interactions in Silver(I) Complexes with α,α′-Diimine Ligands

The allosteric positive cooperativity accompanying the formation of compact [Cu^I(α,α′-diimine)₂]⁺ building blocks contributed to the historically efficient synthesis of metal-containing catenates and knotted assemblies. However, its limited magnitude can easily be overcome by the negative chelate cooperativity that controls the overall formation of related polymetallic multistranded helicates and grids. Despite the more abundant use of analogous dioxygen-resistant [Ag^I(α,α′-diimine)₂]⁺ units in modern entangled metallo-supramolecular assemblies, a related thermodynamic justification was absent. Solid-state structural characterizations show the successive formation of [Ag^I(α,α′-diimine)(CH₃CN)][X] and [Ag^I(α,α′-diimine)₂][X] upon the stepwise reactions of α,α′-diimine=2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives with AgX (X=BF₄⁻, ClO₄⁻, PF₆⁻). In room-temperature, 5–10 mM acetonitrile solutions, these cationic complexes exist as mixtures in fast exchange on the NMR timescale. Spectrophotometric titrations using the unsubstituted bpy and phen ligands point to the statistical (=non-cooperative) binding of two successive bidentate ligands around Ag^I, a mechanism probably driven by the formation of hydrophobic belts, that overcomes the unfavorable decrease in the positive charge borne by the metallic cation. Surprisingly, the addition of methyl groups adjacent to the nitrogen donors (6,6′ positions in dmbpy; 2,9 positions in dmphen) induces positive cooperativity for the formation of [Ag(dmbpy)₂]⁺ and [Ag(dmphen)₂]⁺, a trend assigned to additional stabilizing interligand interactions. Adding rigid and polarizable phenyl side arms in [Ag(Brdmbpy)₂]⁺ further reinforces the positively cooperative process, while limiting the overall decrease in metal–ligand affinity.     

Induced-Fit Recognition of CCG Trinucleotide Repeats by a Nickel–Chromomycin Complex Resulting in Large-Scale DNA Deformation

Small-molecule compounds targeting trinucleotide repeats in DNA have considerable potential as therapeutic or diagnostic agents against many neurological diseases. Ni^II(Chro)₂ (Chro=chromomycin A3) binds specifically to the minor groove of (CCG)_n repeats in duplex DNA, with unique fluorescence features that may serve as a probe for disease detection. Crystallographic studies revealed that the specificity originates from the large-scale spatial rearrangement of the DNA structure, including extrusion of consecutive bases and backbone distortions, with a sharp bending of the duplex accompanied by conformational changes in the Ni^II chelate itself. The DNA deformation of CCG repeats upon binding forms a GGCC tetranucleotide tract, which is recognized by Ni^II(Chro)₂. The extruded cytosine and last guanine nucleotides form water-mediated hydrogen bonds, which aid in ligand recognition. The recognition can be accounted for by the classic induced-fit paradigm.     

Recirculation—a novel approach to quantify interstitial analytes in living tissue by combining a sensor with open-flow microperfusion

We report a novel approach to quantify interstitial analytes in living tissue by combining open-flow microperfusion (OFM) with a sensor and the re-circulation method. OFM is based on the unrestricted exchange of molecules between the interstitial fluid (ISF) and a perfusion medium through macroscopic perforations that enables direct access to the ISF. By re-circulating the perfusate and monitoring the changes of the analytes’ concentration with a sensor, the absolute analyte concentration in the ISF can be calculated. In order to validate the new concept, the absolute electrical conductivity of the ISF was identified in six subjects to be 1.33?±?0.08 S/m (coefficient of variation CV?=?6 %), showing the robustness of this approach. The most striking feature of this procedure is the possibility to monitor several compounds simultaneously by applying different sensors which will allow not only the determination of the concentration of a single substance in vivo but also the simultaneous dynamics of different analytes. This will open new fields in analytical chemistry, pharmacology, as well as clinical experimental research.     

Stereoselective cyanation of chiral α-amino aldehydes by reaction with Nagata's reagent: a route to enantiopure β-amino-α-hydroxy acids

Chiral α-dibenzylamino aldehydes react with diethylaluminum cyanide leading to anti-β-dibenzylamino-α-hydroxycyanides as the major diastereoisomers in good yields and diastereomeric excesses. Hydrolysis of the nitrile derivatives allows the synthesis of enantiopure β-amino-α-hydroxy acids.     

Asymmetric Michael addition of boronic acids to a γ-hydroxy-α,β-unsaturated aldehyde catalyzed by resin-supported peptide

A resin-supported peptide catalyst effective for the asymmetric Michael addition of boronic acids to (E)-4-hydroxybut-2-enal was developed. From a spectral study, it was revealed that the optimum peptide consisted of both a β-turn and helix. Such a combination of secondary structures was essential for achieving a high catalytic ability.     

Asymmetric 1,4-addition of organoboronic acids to α,β-unsaturated ketones and 1,2-addition to aldehydes catalyzed by a palladium complex with a ferrocene-based phosphine ligand

A combination of palladium with ferrocene-based phosphine ligand with a carbon–bromine bond was found to be a good catalyst for the 1,4-addition of arylboronic acids to α,β-unsaturated ketones and the 1,2-addition to aldehydes. Using Pd(dba)₂ and (S,R_p)-[1-(2-bromoferrocenyl)ethyl]diphenylphosphine (S,R_p)-1, 3-phenylcyclohexanone was obtained from the reaction of 2-cyclohexen-1-one with phenylboronic acid in the presence of K₂CO₃ in toluene at room temperature after 3 h in 92% yield with 76% ee. In the 1,2-addition of 4-methylphenylboronic acid to benzaldehyde, 96% of (4-methylphenyl)phenylmethanol was afforded after 24 h, while the enantiomeric excess was only 6%.     

Two-Way Catalysis in a Diels–Alder Reaction Limits Inhibition Induced by an External Electric Field

Oriented external electric fields (EEFs) act as catalysts that can induce selectivity in chemical reactions. The responses of the Diels–Alder (DA) reaction between butadiene and ethylene (BDE-DA) as well as cyclopentadiene and ethylene (CPDE-DA) towards EEF stimuli are investigated here using density functional theory (B3LYP) calculations. EEF is a vector that catalyzes the reaction in one direction while inhibiting it in the opposite direction. Here we report that the inhibitive direction becomes rate-enhancing after some increase in the EEF. The EEF value that brings about the maximum possible inhibition for the reaction is defined as the electrostatic resistance point (ERP). The possibility of both normal and inverse electron-demand DA reactions causes catalytic activity in both directions of the EEF starting at a unique ERP value. The C5 substituents of cyclopentadiene control the ERP values depending upon the resistance power that the functional group provides against the EEF. The endo and exo diastereomeric transition states of the DA reaction have distinct ERP values and the difference (ΔERP) provides the through-space electrostatic contribution to the stereoselectivity on a relative scale. Thus, the ERP values can be used as a gauge for the electrostatic interactions between substituent groups and external stimuli.     

Hexabenzocoronene Graphitic Nanocoils Appended with Crown Ethers: Supramolecular Chirality Induced by Host–Guest Interaction

We have designed and synthesized two new achiral hexa-peri-hexabenzocoronene (HBC) derivatives, HBC^CE and HBC^TEG-CE , which bear the crown ether as the pendant for the amino acid binding site. The HBC^CE self-assembled into a racemic mixture of P- and M-handed helical nanocoils, however, in the presence of chiral amino acid guests, it formed helical nanocoils with one-handed screw sense. The effects of the concentration, type and configuration of the guests on the induced circular dichroism (ICD) during the co-assembly of HBC^CE with chiral amino acids were also investigated. Additionally, after complete removal of the chiral guests, the optically active nanocoils did not racemize, even in the presence of excess amino acids with the opposite configuration. In contrast, HBC^TEG-CE with a long triethylene glycol (TEG) chain between the crown ether group and the HBC unit did not exhibit ICD during the co-assembly with chiral amino acids.     

Cyclodextrins in Polymer Synthesis: Free Radical Polymerization of a tert-Butylmethacrylate-Cyclodextrin Host–Guest System in Aqueous Medium

The homopolymerization of methylated-β-cyclodextrin (me-β-CD) host–guest compound of tert-butyl methacrylate (1a) is described. We investigated the free radical polymerization of the complexed monomer (1a) and of the free monomer (1) at ambient and high temperature. Poly(tert-butylmethacrylate) synthesized via the cyclodextrin mediated method exhibited number-average molecular weights ranging from 12,000–60,000 g/mol with polydispersities from 1.9–3.1. The polymerizations without cyclodextrin show significantly lower yields in comparison with the cyclodextrin mediated polymerizations. Here, the polymer obtained is colloidal dispersed. At ambient temperature (20°C) no polymerization occurs in the absence of cyclodextrin, whereas, under the same conditions, the homopolymerization of the complexed monomer (1a) leads to polymerization with yields around 75%.     

Communication: Synthesis of 3-O-Benzyl-β-L-Arabinofuranose 1,2,5-Orthopivalate as a Starting Monomer for Ring-Opening Polymerization

We have studied the ring-opening polymerizations of a variety of glucose orthoester derivatives and found that substituents on the monomer play an important role in stereo- and regioregularity of the resulting polymers.^1-3 These substituent effects open the possibility of application to ring-opening polymerizations of other sugar orthoesters to give stereo- and regioregular polysaccharides. Additionally, the ring-opening polymerization of the galactose orthoester derivative⁴ gave stereoregular (1→5)-β-D-galactofuranan.     

Porpholactams and chlorolactams: replacement of a β,β'-double bond in meso-tetraphenyl-porphyrin and -chlorin by a lactam moiety

Reaction of meso-tetraphenylporpholactone with hydrazine converts the lactone moiety to an N-aminolactam. It also reduces the opposite pyrrolic moiety of both the starting material and the N-aminolactam, generating chlorin-like chlorolactone and N-aminochlorolactam, respectively. Reductive N-N cleavage of the N-aminoporpholactam generates the parent porpholactam.     

Double Asymmetric Core Optimizes Crystal Packing to Enable Selenophene-based Acceptor with Over 18 % Efficiency in Binary Organic Solar Cells

Side-chain tailoring is a promising method to optimize the performance of organic solar cells (OSCs). However, asymmetric alkyl chain-based small molecular acceptors (SMAs) are still difficult to afford. Herein, we adopted a novel asymmetric n-nonyl/undecyl substitution strategy and synthesized two A-D₁A′D₂-A double asymmetric isomeric SMAs with asymmetric selenophene-based central core for OSCs. Crystallographic analysis indicates that AYT9Se11-Cl forms a more compact and order intermolecular packing compared to AYT11Se9-Cl , which contributed to higher electron mobility in neat AYT9Se11-Cl film. Moreover, the PM6 : AYT9Se11-Cl blend film shows a better morphology with appropriate phase separation and distinct face-on orientation than PM6 : AYT11Se9-Cl . The OSCs with PM6 : AYT9Se11-Cl obtain a superior PCE of 18.12 % compared to PM6 : AYT11Se9-Cl (17.52 %), which is the best efficiency for the selenium-incorporated SMAs in binary BHJ OSCs. Our findings elucidate that the promising double asymmetric strategy with isomeric alkyl chains precisely modulates the crystal packing and enhances the photovoltaic efficiency of selenophene-incorporated SMAs.     

Cholesterol conversion to δ4 -cholestenone by cholesterol oxidase in polyphasic systems : extension to the selective oxidation of 7β-hydroxycholesterol

The preparative use of cholesterol oxidase has been extended to polyphasic systems. The enzyme is active in microemulsions with the organic phase composed of mixtures of cyclohexane and chloroform. The kinetic data for oxidation of 7α- and 7β-hydroxycholesterol in microemulsion with the enzyme from Streptomyces are similar to those of cholesterol. The cholesterol oxidase is active in the two phase system aqueous buffer - butyl acetate and the preparative enzymic conversion of 7β-hydroxycholesterol to Δ⁴-7β-hydroxycholestenone was performed in this medium. The enzymic conversion of cholesterol to Δ⁴-cholestenone was also performed in two liquid-solid systems, in buffer with cholesterol adsorbed on silica gel and in organic medium with cholesterol oxidase and catalase entrapped in Chromosorb.     

α-Nitro-β-iodo(sulfanyl)ethenes in reactions with N,S-binucleophiles

α-Nitro-β-iodo(sulfanyl)ethenes were brought into reactions with N,S-binucleophiles that completed with the replacement of the β-functional group. Iodonitroethenes with thiourea and N,N′-diphenylthiourea provided products of S-substitution. The reaction of less reactive sulfanylnitrostyrene with N,N′-diphenylthiourea and also of iodonitrostyrene with 5-amino-benzothiazolyl-2-thiol required longer time and led to the formation of more stable products of N-substitution. The reactions with 5-aminobenzothiazolyl-2-thiolate in all events resulted in the products of S-substitution.     

α,β-Unsaturated Derivatives of Trivalent Phosphorus in Reactions with Activated Carbonyl Compounds

Abstract

Dialkyl alkynylphosphonites (I) react with esters and nitriles of α-oxocarboxylic acids to give phosphorylated alkanoates, 1,3,2-dioxaphospholanes and l-phosphabicyclohept-4-enes, depending on the nature of the reagent and conditions of the reaction. The reaction of dialkyl alkenylphosphonites (II) with esters and nitriles of α-oxocarboxylic acids predominantly leads to dioxaphospholane derivatives.     

A New Approach to C60-Containing Polyphosphazenes by Polymerization of Phosphonitrile Chloride Trimer in the Presence of C60

A novel synthetic strategy was developed to prepare polyphosphazenes containing C60 moieties. Thus, the phosphonitrile chloride trimer underwent thermal ring-opening polymerization （ROP） in the presence of C60 molecules to yield the reactive macromolecular intermediate, C60-containing poly（dichlorophosphazene）. And then, the other groups could be linked to the phosphazene backbone by nucleophilic substitution reaction of the chlorine atoms in this intermediate to produce a series of C60-containing polyphosphazene. The polymer exhibits good solubility in common organic solvents and is thermally stable.     

Metal Catalyzed Polymerization: From Stereoregular Poly(α-olefins) to Tailor-Made Biodegradable/Biorenewable Polymers and Copolymers

Metal catalyzed polymerizations are among the most important chemical reactions, accounting for the production of about 400 million tons per year of polymeric materials, 50 % of which are polyolefins. The CIRCC research units at the University of Salerno, founded by the late Professor Adolfo Zambelli, a coworker of Giulio Natta and a pioneer in the studies of stereospecific polymerization catalysts, has a consolidated expertise in this field. Although often considered a “mature” area of research, olefin polymerization catalysis continues to drive great interest of both industrial and academic scientists. On the other hand, strong political and economic pressure toward the development of “green” and possibly biodegradable alternatives to olefin-based polymers stimulated our group to direct increasing research efforts in the area of sustainable polymers. In this perspective, we focus on the most recent work from the CIRCC research units involved in homogeneous catalysis for polymerization of a variety of monomers, with the aim to address how the concepts and the expertise developed for olefin polymerization can be applied to the development of different metal-catalyzed polymerizations and copolymerizations. Of course, although the results are discussed in the frame of the most important literature contributions, a comprehensive review of such a wide and diversified topic is out of the scope of the paper. References to reviews covering the different types of metal catalyzed polymerizations are provided in each chapter.     

Induced preference for axial chirality in a triarylmethylium o,o-dimer upon complexation with natural γ-cyclodextrin: strong ECD signaling and fixation of supramolecular chirality to molecular chirality

The ratio of the easily interconverting rotational isomers of biphenyl-2,2'-diylbis[bis(4-dimethylaminophenyl)methylium] (R)/(S)-1a(2+) can be biased to prefer an R configuration upon 1:1 complexation with γ-cyclodextrin in water. Through the reaction with Na(2)S, the preference of 1a(2+)@γ-CyD for an axial chirality of R can be fixed as the M-helicity of dihydrothiepin 2.     

Enantioselective Michael addition of α,α-disubstituted aldehydes to nitroolefins catalyzed by a pyrrolidine-pyrazole

An efficient protocol for the asymmetric catalytic Michael additions of α,α-disubstituted aldehydes to nitroolefins with a pyrrolidine-pyrazole is described. The desired products γ-nitrocarbonyl compounds possessing an all-carbon quaternary center, were obtained in good yields and with high levels of enantioselectivities under solvent-free reaction conditions, employing benzoic acid as an additive.