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ANALYTICAL CHEMISTRY417 Doi:10.2533/Chimia.2007.417 CHIMIA 2007, 61,No WERNER PRIZE 2007/GRAMMATICAKIS-NEUMANN PRIZE 2007/ANALYTICAL CHEMISTRY417 doi:10.2533/chimia.2007.417 CHIMIA 2007, 61,No. 7/8 Werner Prize 1 Gramaticakis –Neumann Prize 2007 2 From Simplicity to Complexity via Subcomponent Self-Assembly Photoinduced functions in multicomponent molecular systems Jonathan Nitschke,Marie Hutin, David Schultz,RupamJ.Sarma, SerenaSilvi,Alberto Credi* Victoria E. Campbell, Gérald Bernardinelli Dipartimento di Chimica G. Ciamician, Università degli Studi di Bologna, Organic ChemistryDepartment, University of Geneva, 30 quai Ernest- via Selmi 2, I-40126 Bologna,Italy Ansermet, 1211 Genève 4 Light-induced processesare at the basis of fundamental natural phenomena Thecreation of complexstructures from simple building blocks via ther- as wellasofavariety of applications.Since thefunctions that can arise modynamic self-assembly requires an understanding of the rules followed from the interaction between light andmatterdependonthe degreeofcom- duringthe self-organizationprocess. Since theinceptionofthisresearch plexity and organizationofthe receiving matter, theresearch on these program in August2003, we have sought to identify theserules and to apply processeshas progressively moved frommoleculartosupramolecular(mul- themtosynthetic problems.Subcomponent self-assembly1 describessys- ticomponent) systems.Examples of multicomponent systems capable to tems in which simple amines and aldehydesmay be induced to come to- perform specific functions under light stimulation (photochemical molecular gether around metal-ion templates via the formation of imine (C=N) devices, PMDs)have been developed [1], relying on processessuch as pho- bonds. 2,3 We have thus been abletocreatecomplex structures such as a toisomerization and photoinduced electron or proton transfer. 4 catenane (below, right) or apair of helical molecules linked at aright angle Herewewill describeafew recent examples of PMDs studied in our labora- through metal coordination (below,left),having atertiarystructuresimilar tories[2],designed to (i)processbinaryinformation (molecular logic gates to that of aprotein. Thesestructures arecapable of dynamic reassembly at 5 andcircuits)or(ii) undergo controllablemotions of some molecular com- both NMetal and C=Nlinkages. ponentswith respect to the others(molecular machines). Apart from futuristic applications,investigations on PMDs can increasethe H H N basic understanding of avariety of processes, as well as develop reliable N theoretical models.Thisresearch hasalsothe important merit of stimulating O O theingenuity of chemists,thereby instilling newlifeinto chemical sciences. N N N Cu+ N N Cu+ N N N O O [1] V. Balzani, A. Credi, M. Venturi, Molecular Devices and Machines , Wiley-VCH, Weinheim, 2003.A.Credi, Aust.J.Chem. 2006, 59,157. N H H N [2]V.Balzani,M.Clemente-León, A. Credi,B.Ferrer, M. Venturi, A.H. 1. J.R. Nitschke Acc. Chem.Res. 2007,40, 103 Flood, J.F. Stoddart, Proc. Natl.Acad. Sci.USA 2006, 103,1178.R. 2. J.R. Nitschke,M.Hutin,G.Bernardinelli Angew. Chem.Int.Ed. 2004,43, 6724 Ballardini, A. Credi, M.T. Gandolfi, F. Marchioni, S. Silvi, M. Venturi, 3. M. Hutin, G. Bernardenelli,J.R.Nitschke Proc.Natl. Acad. Sci. USA 2006,103, 17655 Photochem. Photobiol.Sci. 2007, 6 ,345.S.Silvi,E.C.Constable, F.M. 4. M. Hutin, C.A. Schalley,G.Bernardinelli,J.R.Nitschke Chem.Eur.J. 2006,12, 4069 Raymo, A. Credi, submitted. 5. D. Schultz,J.R.Nitschke Proc.Natl.Acad. Sci. USA 2005,102, 11191 Analytical Chemistry 3 Analytical Chemistry 4 Snapshots of aheterogeneous catalystatwork: From integral Chemometrictoolstosimplifymethoddevelopment:screeningofdop- towardsspatially resolved spectroscopicmonitoringofsolid materials ing agentsinurinary samples. Jan-DierkGrunwaldt1 ,Stefan Hannemann1 ,BertramKimmerle1 , Ivano Marchi,Serge Rudaz, Jean-LucVeuthey Alfons Baiker1 ,Pit Boye2 ,JensPatommel 2 ,Christian G. Schroer2 LaboratoryofAnalytical Pharmaceutical Chemistry, School of Pharmaceu- 1 Institute forChemical andBioengineering, Department of Chemistry and tical sciences,University of Geneva, University of Lausanne, Bd d'Yvoy 20, Applied Biosciences,ETH Zurich, Hönggerberg, HCI, CH-8093 Zürich 1211 Geneva 4, Switzerland 2 Institute of Structural Physics,TUDresden, D-01062 Dresden Analysesinanti-doping control occur in two steps. First,ageneric To gain information on the structureofsolidmaterials such as heterogene- fast screening analysis is used to determinethe presence of alarge number ouscatalysts,insitu X-rayabsorption spectroscopy (XAS)isawell-suited of forbidden compounds in urine. Second,inthe caseofpositive result, a technique. In certain processesthe structureofacatalystmay varyalong a specific procedure(confirmatoryanalysis)has to be performed to quantify catalytic reactor particularly if prominent gradients in temperatureorcon- thesubstance(s). centration occur.The investigation of these phenomena requires spatially Screening method development is tedious and time consuming due resolved techniques on amicroscale. to the necessity to optimizethe sample preparation of alarge quantity of Here we present structural data of noblemetal catalysts during partial oxida- compounds.The useofchemometric toolsisthereforeproposed to reduce tionofmethane (CPO). To efficiently recordXAS spectra in alocally re- the number of tested analytes in method development by choosing represen- solved way, anew approach is suggestedusing aCCD-camera[1].The re- tative compounds of the whole set. sults arecomparedtothosefromXAS-measurements. In addition,the In this study, agroup of thirty-sixdoping agents consisting of diuretics temperaturegradientwas determined usinganinfraredcamera[2].Acor- and beta-blockerswas used. Astandardsolution containing all analytes was relation between the structure of the catalyst, the catalytic data andthe axial loaded, washed and eluted with four different SPEsorbents.All fractions temperatureprofile in the catalytic reactor was established. Tremendous were collected and each compound wasretrieved by LC-ESI-MS. In order structural changes of the noble metal particles within agradient of lessthan to bringout differences among compounds,amultivariate analysis approach 100 mm thicknessand astrong dependence of thegradient on the reaction was used. Asmall number of groups emerged and subsequent method de- conditions (temperature, space velocity)wereobserved. Veryrecently, velopment was performed by selecting representative compounds in the "snapshots" werenot only taken of the variation in catalyststructureand obtained clusterisation. temperature, but we even succeeded in following thesechanges in a time-resolvedmannerusing aCCD-and an IR-camera. [1]J.-D. Grunwaldt, S. Hannemann, C.G. Schroer, A. Baiker, J. Phys. Chem. Lett. B 2006, 110, 8674; J.-D.Grunwaldt, S. Hannemann, A. Baiker, P. Boye,C.G. Schroer,Highlights of Analytical Chemistry, Chimia 2006, 60, 709. [2]S.Hannemann, B. Kimmerle, J.-D.Grunwaldt, A. Baiker, P. Boye,C.G. Schroer,inpreparation. ANALYTICAL CHEMISTRY418 CHIMIA 2007, 61,No. 7/8 Analytical Chemistry 5 Analytical Chemistry 6 Microchip electrophoresis bioanalytical applications Development of amethodtocharacterize nanoparticle uptakeinto Corn plants Marketa Vlckova, MariaA.Schwarz Karin Birbaum 1 ,RobertBrogioli1 ,Ludwig Limbach2 ,EnricoMartinoia3 , University of Basel, Spitalstrasse 51, 4056 Basel, Switzerland Wendelin Stark 2 ,Detlef Günther1 Theimplementation of microfabricated separation devices (socalledmicro- 1 LaboratoryofInorganic Chemistry, ETH Zurich,Wolfgang-Pauli Strasse chips)inelectrophoresis has become atrend in modernseparation science. 10, 8093 Zurich,Switzerland However,the miniaturization of the separation to microchip brings along 2 Institute for Chemical andBioengineering,ETH Zurich, Wolfgang-Pauli some benefits (speed,negligible consumption of substances or high Strasse 10, 8093 Zurich,Switzerland throughput analysis)alsosome drawbacks(limited separation efficiency and 3 Laboratoryfor Molecular Plant Physiology, University of Zurich,Zolliker- selectivity, higherdetection limits or the absenceofautomation). strasse 107, 8008 Zurich, Switzerland Nevertheless, in some applicationareas theadvantages of themicrochip separations overcome the limitations.Adevelopmentofaselective andsen- Nanoparticles (NP) areincreasingly used in various applications e.g. as sitive detection, often involving expensive reagents,orafast development catalysts or millingagents.Thereforerisks of exposureduring production of aseparation method could be listed as the examples of such applications. processesand distribution in the environment requireclarification about the Specificmeasurementsfor particular purposes (affinity measurementsand potentialrisks.Studies using human lung cellshaveshown that agglomera- other)represent then further useful applications of microchips tion, sedimentation and diffusion of NP affect uptake by cells [1]. This Thelisted applications areas of microchips willbedemonstrated by present- study has investigated the uptake of CeO 2 NP during exposuretoairborne ing the results of our research.The sensitivity of amperometric detection of NP into Corn plants. catecholamines has been specifically enhanced with thehelpofenzymes [1] Forthe experiments,the plants wereplaced in aglove box that allowed the andalsocarbon nanotubes [2]. Acomplex separation method has been de- production of NP flame spraysynthesis in situ forashortduration (~1min). veloped forsimultaneous separation of allthree catecholamines and their TheNPare distributed within the glove box by afan.The plants remain
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