News

Stanford, Plflughaupt and Dove have reported the synthesis of stereoregular cyclic poly(lactide)s using an A₂ + B₂ couplingof a telechelic malemide-functional poly(lactide) with ethanedithiol. The group went on to show that the incorporation of a disulfide bridge in the macrocycles could be cleaved selectively upon addition of PBu₃ with the excipient thiol being trapped with N-methyl maleimide to provide a site for selective polymer modification. See the full communication at:

 http://pubs.acs.org/doi/abs/10.1021/ma101291v

The improved synthesis of a cyclic ester monomer, 3-(S)-[(benzyloxycarbonyl)methyl]-1,4-dioxane-2,5-dione (BMD) from commercially available L-malic acid as a renewable feedstock is reported. Organocatalyzed ring-opening polymerization of BMD enables the controlled ROP of this monomer without deleterous transesterification side reactions, despite the presence of side-chain esters. The report also details studies into the effect of initiating species as well as the degradation behaviour of the deprotected hydrophilic poly(glycolic-co-malic acid)s (http://pubs.acs.org/doi/abs/10.1021/bm1004355)

The Bon polymer colloids group won 3 prestigious poster awards at the 43th IUPAC World Polymer Congress held at the SECC in Glasgow UK, july 11-16th 2010. PhD student Nick Ballard was awarded the Akzo Nobel poster price for outstanding work. PhD students Andrew Edwards and Rong Chen both were awarded the Akzo Nobel poster prices for excellent contributions. Group leader assoc. prof. Stefan Bon said: " We are honoured and absolutely delighted that our research was awarded these poster prices. We already had a fantastic time at Macro2010, but this absolutely tops it! We would like to thank all for showing interest in our work, and especially Akzo Nobel for sponsoring these poster awards." More info on the Bon polymer colloids group

This scanning tunnelling microscopy (STM) and density Functional Theory (DFT) study reports on the formation of chiral domains self-assembled from terephthalic acid (TPA) and iron on a Cu(110) surface (http://pubs.acs.org/doi/abs/10.1021/jp101439z). The supramolecular structures are organized on successive hierarchical levels with chiral properties developing only at the latest assembly step. The driving forces for the generation of these high-order chiral architectures are identified as competing coordination bonding within the metal-organic complexes and hydrogen bonding among them.

Date:	Tuesday 20 July 2010
Time:	2pm to 6pm
Location:	MS01, Mathematics Institute
Open To:	Everyone
Cost:	Free
Summary:	Symposium to celebrate the award of honorary degrees to Professor Bob Grubbs and Professor Richard Lerner.   Programme: Chair: Professor Dave Haddleton 2pm Professor Bob Grubbs, California Institute of Technology 3pm Dr Andrew Dove, University of Warwick, Department of Chemistry 3:30pm Coffee Chair: Professor Greg Challis 4pm Dr Emma Anderson, University of Warwick, Department of Biological Sciences 4:30pm Professor Richard Lerner, Scripps Research Institute 5:30pm Reception

Studies of the reactions of this Ru^II tetrahydroanthracene anticancer complex with DNA by 2D NMR and HPLC-MS reveal penetrative DNA intercalation and G-base selectivity.

Penetrative DNA intercalation and G-base selectivity of an organometallic tetrahydroanthracene Ru^II anticancer complex
Hong-Ke Liu, John A. Parkinson, Juraj Bella, Fuyi Wang and Peter J. Sadler,  Chem. Sci., 2010
DOI: 10.1039/c0sc00175a

 

JENKINS’ REVIEW LECTURE NOW PUBLISHED, VBT PAPER APPEARS IN ACS “MOST CITED” LIST.

 

Emeritus Professor H. Donald B. Jenkins’ Exaugral Lecture, given during the Symposium held by the Department in his honour, has now been published.

 

Jenkins is involved in the establishment of a new approach to obtain, simply, thermodynamic data for inorganic compounds using x-ray diffraction data or density. His key paper on Volume-Based Thermodynamics (VBT) Approach (which was Inorg. Chem.,1999, 38, 3609-3620), is currently listed among the ACS “300 most frequently cited papers over the last three years” on the ACS website. Colleagues can now also read an account of Jenkins’ work in the context of his earlier work, as given in his symposium talk, which has appeared in Science Progress. 

http://dx.doi.org/10.3184/003685009X458660

 

 

THE “DIFFERENCE RULE“INCLUDED IN SIR JOHN ROWLINSON’S CELEBRATORY AMERICAN CHEMICAL SOCIETY. ISSUE.

Professor Jenkins and co-workers continue to extend their Thermodynamic Difference Rule

Thermodynamic data are required in order to understand the behaviour of materials, but are often lacking (or even unreliable) for a variety of reasons such as synthetic problems, purity issues, instability etc. In an ACS, invited paper, for the Sir John Rowlinson, F.R.S. Festschrift (Celebratory Issue) the Thermodynamic Difference Rule (TDR) is highlighted. Developed here at Warwick (J. Amer. Chem.Soc., 2004, 126, 15809-15817 ), TDR is a rule whose purpose is to predict with - reasonable accuracy - standard thermodynamic data (eg.  D_fH^o, D_fG^o, D_fS^o or S^o₂₉₈ etc.) for hydrates and solvates which is currently needed. The rule uses existing known thermodynamic data either for the parent salts from which these hydrates/solvates are derived or from other hydrates/solvates.

http://dx.doi.org/10.1021/je100383t

Abstract: The use of poly(lactide)-based materials is, in part, limited by their physical and mechanical properties. This article reviews the methods that have been employed to enable enhancement of the materials properties through synthetic manipulation of the polymer structure including block copolymer synthesis and modification of the lactide monomer structure, focusing on the application of ring-opening polymerization. In turn the effect of these structural modifications on the properties of the resultant materials are reported. 

Link: http://www3.interscience.wiley.com/journal/123576544/abstract 

Biological antifreezes are a relatively large and diverse class of proteins  which are capable of interacting with ice crystals to prevent their growth. These properties allow for the survival of organisms which live at subzero temperatures,  and would otherwise lead to cryo-induced death. In this review article, the application of synthetic polymers as mimics of antifreeze glycoproteins is introduced.

Link
http://dx.doi.org/10.1039/C0PY00089B

Richard Walton is co-editor of a new book series, Inorganic Materials, with Duncan Bruce (University of York) and Dermot O’Hare (University of Oxford). The first volume, Functional Oxides, was published on June 11th by Wiley and four further volumes will appear during 2010.

 

 

http://www.wiley-vch.de/publish/en/books/bySubjectMS00/forthcomingTitles/0-470-99750-8/?sID=vr779f87qauogpb4gg0umkrg80

Sarah Crosby, working in Jon Rourke's group, has identified a number of new Pt(IV) complexes containg dmso ligands.

Oxidation of cyclometalated Pt(II) complexes with S-bound DMSO ligands initially results in Pt(IV) complexes which retain the S-bound DMSO ligands in the same relative position. Isomerisation reactions result in a rearrangement of the ligands to give O-bound DMSO complexes, with the DMSO trans to a cyclometalated carbon. X-ray structures representing the only two known examples of Pt(IV) complexes with O-bound DMSO ligands have been solved. The rate of isomerisation of complexes without a pendant alkyl chain is strongly solvent dependent, consistent with the need to stabilise a coordinatively unsaturated intermediate. Pt(IV) complexes with a pendant alkyl chain show little dependence on isomerisation rate with solvent, with solution NMR data strongly suggesting the presence of agostic complexes. DFT calculations provide support for the presence of agostic complexes, with the same interactions being used to account for the loss of DMSO from the O-bound DMSO complexes.

See http://pubs.acs.org/doi/pdf/10.1021/om901087m

In this article in Angewandte Chemie, Rodger and coworkers us metadynamics computer simulations to show that the eggshell protein ovocleidin-17 induces the formation of calcite crystals from amorphous calcium carbonate nanoparticles. Multiple spontaneous crystallization and amorphization events were simulated; these simulations suggest a catalytic cycle that explains the role of ovocleidin-17 in the first stages of eggshell formation (the picture shows one intermediate of this cycle).

http://www3.interscience.wiley.com/journal/123506601/abstract