Ring opening polymerization of lactide promoted by alcoholyzed heteroscorpionate aluminum complexes

The alcoholysis of the heteroscorpionate methyl aluminum complex (bpzmp)AlMe₂ ( 1 ) (bpzmp = 2,4‐di‐tert‐butyl‐6‐(bis‐(3,5‐dimethylpyrazol‐1‐yl)methyl)phenoxo), promoted both by phenol and isopropanol, has been investigated. The reaction of 1 with phenol afforded the dimeric mono(phenoxo) derivative 2 , whereas the alcoholysis of 1 with the less acidic isopropanol involved the coordinated heteroscorpionate ligand and led to the tetrahedral complex 3 in which the aluminum atom is surrounded by one κ²‐N,O^? coordinated bpzmp ligand and one η¹‐O^? coordinated ppzmp ligand (ppzmp = 2,4‐di‐tert‐butyl‐6‐(i‐propoxy‐(3,5‐dimethylpyrazol‐1‐yl)methyl)phenoxo). Complexes 1 – 3 have been tested in the ring opening polymerization (ROP) of L ‐lactide. The dimeric mono(phenoxo) derivative 2 was inactive in the ROP of L ‐lactide. Quite surprisingly, complex 3 was found to be active in ROP of L ‐ and rac‐lactide, showing a good molar‐mass control. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3632–3639, 2010     

Rhodium(II)‐Catalyzed Nondirected Oxidative Alkenylation of Arenes: Arene Loading at One Equivalent

A bimetallic Rh^II catalyst promoted the C? H alkenylation of simple arenes at 1.0 equivalent without the use of a directing group. A phosphine ligand as well as cooperative reoxidation of Rh^II with Cu(TFA)₂ and V₂O₅ proved essential in providing monoalkenylated products in good yields and selectivities, especially with di‐ and trisubstituted arenes.     

Heterocyclic systems. VIII. synthesis of 1H,4H-pyrazolo[4,3-f]pyrrolo[1,2-a]azepine derivatives

The synthesis of the unknown title Compounds is described. The preparation involves intramolecular acylation of 3-[1-phenyl-5-(1-pyrryl)pyrazol-4-yl]propanoic acid 9 to the tricyclic ketone 10 , which was then transformed into 1H,4H-pyrazolo[4,3-f]pyrrolo[1,2-a]azepine 12 and its dihydro derivative 13 by reductive procedures.     

Erratum: ‘A copper HyBrlD laser of 120W average output power and 2.2% efficiency’

Erratum: A copper HyBrlD laser of 120W average output power and 2.2% efficiency     

Corrigendum: ‘Output power limitations in CW single transverse mode Nd:YAG lasers with a rod of large cross-section’

Corrigendum: Output power limitations in CW single transverse mode Nd:YAG lasers with a rod of large cross-section     

Carboxylation of a linear low density polyethylene via gamma irradiation in presence of carbon dioxide in subcritical and supercritical conditions

In this work the molecular modifications induced in a linear low density polyethylene gamma irradiated in presence of carbon dioxide both in subcritical and supercritical conditions are presented. The obtained results indicate that this process can be a new and interesting way in order to graft oxidized groups in the polyethylene chains. Moreover it is worth noting that, together with these functionalization reactions, also a significant crosslinking occurs, with improvement in some mechanical tensile behaviour.     

Time-resolved and steady-state fluorescence studies of excited-state proton-transfer reactions of proflavine

Time-resolved and steady-state fluorescence studies of proflavine in aqueous solution are presented. The observation of a monoexponential fluorescence decay with a time constant decreasing with increasing pH and the presence of an anomalous red-shift in the fluorescence spectrum as a function of pH indicate the existence of a complex proton-transfer mechanism in the excited state. A reaction scheme is proposed and the corresponding proton-transfer rates are evaluated. An excited-state pK value of 12.85 is obtained for the equilibrium between the cationic form of proflavine and the same form dissociated at an amino group.     

Three of a Kind: Control of the Expression of Liver-Expressed Antimicrobial Peptide 2 (LEAP2) by the Endocannabinoidome and the Gut Microbiome

The endocannabinoidome (expanded endocannabinoid system, eCBome)-gut microbiome (mBIome) axis plays a fundamental role in the control of energy intake and processing. The liver-expressed antimicrobial peptide 2 (LEAP2) is a recently identified molecule acting as an antagonist of the ghrelin receptor and hence a potential effector of energy metabolism, also at the level of the gastrointestinal system. Here we investigated the role of the eCBome-gut mBIome axis in the control of the expression of LEAP2 in the liver and, particularly, the intestine. We confirm that the small intestine is a strong contributor to the circulating levels of LEAP2 in mice, and show that: (1) intestinal Leap2 expression is profoundly altered in the liver and small intestine of 13 week-old germ-free (GF) male mice, which also exhibit strong alterations in eCBome signaling; fecal microbiota transfer (FMT) from conventionally raised to GF mice completely restored normal Leap2 expression after 7 days from this procedure; in 13 week-old female GF mice no significant change was observed; (2) Leap2 expression in organoids prepared from the mouse duodenum is elevated by the endocannabinoid noladin ether, whereas in human Caco-2/15 epithelial intestinal cells it is elevated by PPARγ activation by rosiglitazone; (3) Leap2 expression is elevated in the ileum of mice with either high-fat diet—or genetic leptin signaling deficiency—(i.e., ob/ob and db/db mice) induced obesity. Based on these results, we propose that LEAP2 originating from the small intestine may represent a player in eCBome- and/or gut mBIome-mediated effects on food intake and energy metabolism.     

Vibrational analysis for surge precursor definition in gas turbines

Compressor behaviour analysis in critical working conditions, such as incipient surge, represents a significant aspect in the turbomachinery research field. Turbines connected with large-size volumes present critical issues related to surge prevention especially during transient operations. Investigations based on acoustic and vibrational measurements appear to provide an interesting diagnostic and predictive solution by adopting suitable quantifiers calculated from microphone and accelerometer signals. For this scope a wide experimental activity has been conducted on a T100 microturbine connected with different volume sizes. A machine dynamical characterisation has been useful for better interpretation of signals during its transient to the surge. Hence, different possible methods of incipient surge identification have been developed through the use of different signal processing techniques in time, frequency and angle domain. These results will be useful for control system development to prevent compressor failures.

     

Tin(IV), Monomethyltin(IV), and Dimethyltin(IV) Complexes with thiol sulfur and heterocyclic nitrogen donors: Molecular dynamics and structure by 119Sn mössbauer spectroscopy

The molecular dynamics of the complexes Sn(SPyN)₄ ( 1 ), SnCl₂(SPyN)₂ ( 2 ), MeSn(SPy)₃ ( 3 ), MeSnCl(SPyN)₂ ( 4 ), Me₂Sn(TCy)₂ ( 5 ), Me₂SnCl(TOx) ( 6 ), and Me₂Sn(TUr) ( 7 ) [HSPy = 2-mercaptopyridine; HSPyN = 2-mercaptopyrimidine; HTCy = 2-thiocytosine; HTOx = 8-thioquinoline; H₂TUr = 2-thiouracil] has been investigated by variable temperature ¹¹⁹Sn Mössbauer spectroscopy. The area under the resonant peaks has been determined as function of temperature, from which Debye temperatures and cut-off frequencies, as well as recoil-free fractions (Lamb Mössbauer factor) and mean square displacements of ¹¹⁹Sn, have been calculated. By fingerprint procedures on the basis of literature data, monomeric structures are attributed to complexes ( 1 )–( 4 ) and ( 6 ), while ( 5 ) and ( 7 ) lie in the borderline monomersmonodimensional polymers. The results are discussed on the basis of known crystal and molecular structures. The nature of the environment of tin atoms has been simulated by point-charge model calculations of nuclear quadrupole splitting parameters; molecular structures are proposed for complexes ( 5 )–( 7 ), where no X-ray diffractometric data are available.