101 - University of Groningen

1 Stratingh Institute for Chemistry Newsletter nr 101— June 2014

Gratama Science Award to Anna Hirsch Anna Hirsch of the Bio-Organic Chemistry group has been chosen as the winner of this year’s competition for the Gratama Science Award. The Gra-tama Science Award is a prize to encourage young scientists who distinguish themselves by their innovative, socially relevant, and challenging research. The Gratama Science Award was installed in 2011 and is awarded each year, alternately to candidates of the universities of Leiden and Groningen, res-pectively. Anna was nominated by our faculty earlier this year. The awar-ding ceremony will be on July 4th, during the University’s traditional ‘Summer ceremony”.

NWO Vidi grant awarded to Tati Fernández The Netherlands Organisation for Scientific Research (NWO) has awarded the prestigious VIDI grant (800,000 €) to M. A. (Tati) Fernández. This award will allow her to lead a research group within the Stratingh Institute for Chemistry for a period of five years. In her project, entitled "New strategies to sustainable procedures based on metal-catalyzed C-H functionalization", she will focus on the development of new catalysts for the direct and selective functio-nalization of C-H bonds, a highly attractive strategy to achieve green, clean and efficient transformations.

Anna Hirsch, together with prof. dr. L. Dijkhuizen, is awarded an

NWO ECHO-STIP grant with her project: “Selective small-molecule inhibitors of glu-

cansucrases as chemical probes and potential toothpaste additives”

Adri Minnaard is awarded a n NWO TOP grant with his project: “Palladium

Catalysis enabling Chemical Biology “

Syuzi Harytyunyan is awarded and NWO ECHO grant with her project:

“Catalytic asymmetric methods for synthesis of diary alcohols, diarylamines and aminoesters

with quaternary stereocenters”

101 June 2014


2nd place Gouden Spatel for Nick Das

In the competition for the Gouden Spatel (Golden Spatula) 2013, the

prize for the best HBO-undergraduate report in chemistry, Nick Das,

trainee in the Bio-organic Chemistry group under the supervision of

Peter Fodran, MSc, and Prof. Dr. Adri Minnaard ended at the second

place and received 250 euro. His thesis is entitled: “Towards the Disco-

very of the Tri-acylglycerol Composition of Milk Fat”

Danny Geerdink awarded the Backer Prize for the best PhD thesis in

Organic Chemistry in The Netherlands 2013

At the Wageningen symposium of the KNCV, it was announced that Dr. Danny

Geerdink, (Prof. Dr. Adri Minnaard and Dr. Anna Hirsch, Bio-organic Chemis-

try) has been awarded the Backer Prize for the best PhD thesis in Organic Che-

mistry in The Netherlands 2013. His thesis is entitled: Total synthesis of enan-

tiopure lipids : on mycobacterial glycolipids and a putative sex pheromone of

Trichogramma turkestanica

Danny Geerdink will give a lecture at the NWO CHAINS meeting in Novem-

ber.

Highlights by Prof. dr. Jan B.F.N.Engberts

Over several decades there has been an enormous fuss about the electronic structure of the 2-

norbornyl cation. In an interesting perspective, both historically and scientifically, Bob Moss

(Rutgers, The State University of New Jersey) describes how finally the bridged or

“nonclassical” structure has been accepted, which features 3-center, 2-electron bonding. Spec-

troscopic and computational studies were perhaps most important in resolving the structural

uncertainties and the results had a great impact on mechanistic aspects of the solvolysis and

ionization of various exo-2-norbonyl substrates. The “nonclassical” structure of the cation was

characterized by Walling as “a corner-protonated cyclopropane”. R.A. Moss, J.Phys.Org.Chem. 2014,

27, 374-379.

Highly strained hydrocarbons have captured the imagination of many chemists because of,

inter alia, their challenging synthesis and material properties. Jasti and colleagues from Bos-

ton University, have now prepared [5]cycloparaphenylene ([5CCP]), a carbon nanohoop, with

structural elements related to C60 and C70. The compound has severely distorted phenyl rings

and a strain energy of 119 kcal.mol-1 has been calculated. The geometry of 5CCP was confir-

med by single-crystal X-ray diffraction. Cyclic voltammetry suggests that 5CCP could well be a

desirable material for organic electronics. P.J. Evans, E.R. Darzi, R. Jasti, Nature Chem. 2014, 6, 404-408.

It is well recognized that the hydroperoxide anion, HO-, plays an important role in many biolo-

gical systems and industrial processes. In contrast to the hydroxide ion, relatively little is

known about the hydration properties of HOO-. Scientists from three American universities

have now performed detailed ab initio molecular dynamics studies of aqueous HOO- in liquid

water. Information was obtained on the electronic structure and hydration characteristics of

the anion. The most important hydration structure contains four hydrogen bond donors to the


terminal oxygen atom and either one or two hydrogen bond donors to the middle oxygen atom. A

comparison has been made with the hydration properties of the hydroxide anion. Z. Ma, D. Anick,

M.E. Tuckerman, J.Phys.Chem.B 2014, DOI 10.1021/jp5008335.

(-)-Lepenine is a denudatine-type alkaloid with a complicated, rigid polycyclic structure. It has

interesting and useful properties, both in chemistry and biochemistry. Its asymmetric total syn-

thesis has now been reported for the first time by synthetic chemists from two Japanese universi-

ties. The hexacyclic system was effectively constructed via a tethered intramolecular Diels-Alder

reaction, an intramolecular Mannich reaction, and a Diels-Alder reaction between an ortho-

quinone monoketal and ethylene. The synthetic procedure also involves a chirality transfer from

L-lactic acid methyl ester via a Claisen rearrangement. The synthetic product was identical in all

respects to natural lepenine. Y. Nishiyama, Y. Han-ya, S. Yokoshima, T. Fukuyama, J.Am.Chem.Soc. 2014, DOI

10.1021/ja503023h.

Carbon-based nanostructures are valuable materials in ultrafast electronics and optoelectronics.

Scientists from three Spanish Institutes and from the University of Strasbourg have now investi-

gated a prototype carbon-based molecular junction consisting of a single C60 molecule and have

analysed how the electric current through the junction depends on the chemical nature of the fo-

remost electrode atom in contact with the molecule. An important factor is the strength of the

metal-C bonds, but it is particularly the chemical valence of the metal atom that determines the

efficiency of injection of charge into an sp2 carbon atom. In case of transition metals, elements in

the centre of the d-block possess a higher ability for charge injection than atoms from the d-block

extrema due to a higher density of states at the Fermi level. T. Frederiksen, G. Foti, F. Scheurer, V. Speis-

ser, G. Schull, Nature Comm. 2014, DOI 10.1038/ncomms4659.

A very unusual solvent effect. Whereas 1,3-dimethylimidazolium-2-carboxylate (1) is stable in

pure water and in pure acetonitrile, it undergoes a rapid decarboxylation/protonation reaction in

mixtures of the two solvents. This challenging behavior was further studied by both kinetics mea-

surements and by density functional theory (DFT) calculations. Falvey and his coworker from the

University of Maryland claim that water has two effects on the stability of 1. At low concentration

in acetonitrile it provides a proton for the trapping of the carbene formed by decarboxylation of 1,

thereby accelerating decomposition. At higher concentrations of water, the polarity of the medi-

um is increased which slows down the decarboxylation and likewise the decomposition rate. D.M.

Denning, D.E. Falvey, J.Org.Chem. 2014, DOI 10.1021/jo5007575.

Thioesters are useful building blocks in organic synthesis and chemical biology. Chemists from

the National Chung Hsing University at Taiwan showed that thioesters can be obtained from an

iron-catalyzed reaction of thiols with aldehydes in water. tert-Butyl hydroperoxide was employed

as an oxidant and the thioesters were obtained in moderate to excellent yields. A large number of

functional groups are tolerated under the reaction conditions. Y-T. Huang, S-Y. Lu, C-L. Yi, C-F. Lee,

J.Org.Chem. 2014, DOI 10.1021/jo500574p.

Among the distinctive properties of graphene are its conductivity, flexibility, and the controllable

permittivity and hydrophilicity. The development of multifunctional biomedical devices takes

advantage of these and other characteristics of this fascinating molecule. As argued by Novoselov

and his colleague from the University of Manchester, further applications of graphene for biome-

dical applications should take into account three layers of complexity: (1) material characteristics,

(2) interactions with biological components (tissues, cells, proteins) and (3) biological activity

outcomes. Only rational, well-designed studies of graphene interactions with cells, tissues and

organisms will help guide the best choices for application of graphene materials. K. Kostarelos, K.

Novoselov, Science 2014, 344, 261-263.

In an issue of J.Phys.Chem.Lett. of a few months ago, the Editor-in-Chief (Schatz) and the Depu-

ty Editor (Kamat) published a useful editorial entitled “How to Make Your Next Paper Scientifi-

cally Effective.” It is noted that not too long ago scientific papers were written in a rather rigid


and conservative format. That has now changed significantly and scientific publications are now

written in a more glamorous way. The authors of the paper give a lot of advice how to compose a

manuscript that is nicely presented, complete and with accurate information. Such a paper will

sail through the review process with a greater chance of success and will be read and more fre-

quently cited by other scientists. In other words, the impact of the paper will be significantly in-

creased. Worth reading this editorial! P. Kamat, G.C. Schatz, J.Phys.Chem.Lett. 2013, 4, 1578-1581.

Best wishes for my readers for a pleasant and relaxing summer holiday!

Jan Engberts

Stratingh Lectures

Tuesday, June 10th , 2014

Dr. Rafal Klajn—Department of Organic Chemistry, Weizmann Insti-tute of Science, Israel

Title: Out-of-equilibrium materials constructed from molecular switches and superparamagnetic nanoparticles

Room: 5111.0022 Time: 16:00

Thursday, June 19th , 2014

Prof.dr. Donald Hilvert—ETH Zürich, Switzerland

Title: Designer Enzymes

Room: 5111.0022 Time: 16:00

PhD Defences

Friday, June 20th

@ 9:00 Jeffrey Bos will defend his PhD thesis. Title: “Artificial Metalloenzymes”. Promotor:

Prof. dr. J.G. Roelfes

Friday, June 20th

@ 16:15 Parisa Pourhossein Aghbolagh will defend her PhD thesis. Title: “The Fabrication of

Nanogap Electrodes Using Nanoskiving”. Promotor: Prof. dr. J.C. Hummelen, Co-promotor: Dr.

R.C. Chiechi

New appointments

Werkbespreking: Thursday morning 8.30 hrs, room 5111.0080

June 5th—Workweek

June 12th—Z. Wu—Synthesis of natural products containing chiral tertiary alcohols

June 19th—S. Varatharajan—N4Py derivatives for targeting specific cell organelles

June 26th—W. H. Chen—Title to be announced

July 3rd—T. van Leeuwen—Mechanochemistry with Molecular Motors

July 10th—S. Perdriau—New reactivities for a well-known PNN ruthenium pincer complex

July17th—J. Edens—Synthesis and biological evaluation of ABPs based on lipocyclocarbamat

July 24th—A. Lubbe—Title to be announced

July 31st—S. Abdolahzadeh—Catalysis in complex media

If you have items for the next issue of this Newsletter, please send an e mail to the Stratingh Institute

office: [email protected]

The next issue of the Stratingh newsletter will appear in September 2014.

1/4/2014—PostDoc

Vijayendar Reddy Yedulla

Group Minnaard

16/5/2014—PhD

Dorus Heijnen

Group Feringa

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101 - University of Groningen