Molecular Clustering by High Resolution NMRAmong all self-aggregation processes, the selfaggregationof lipid molecules to form bilayermembranes is a process fundamental to theorganization of life. Thanks to their spontaneoustendency to aggregate, some lipid moleculesconstitute local phases of highly concentratedorganic compounds, embedded in the membrane andtherefore could enhance concentration dependentchemical interactions.temperature dependence has given us usefulinformation on clusters formation, making itsdependence on temperature and gangliosideconcentration more clear.References[1] D’Emiliano D., Casieri C., Paci M. and De Luca F.2006. Detection of Ganglioside Clustering in DOPCBilayers by 1H-NMR Spectroscopy. PhysicaA (2006),doi:10.1016/j.physa.2006.07.021.AuthorsD. D’Emiliano (a,b), C. Casieri (a,c) and F. De Luca(a,b).(a) CRS SOFT-INFM-CNR, Roma, Italy(b) Dip. <strong>di</strong> <strong>Fisica</strong>, Univ. <strong>di</strong> Roma La <strong>Sapienza</strong>, Roma,I(c) Dip. <strong>di</strong> <strong>Fisica</strong>, Università <strong>di</strong> L’Aquila, L’Aquila, IFig. 1: The appearance of the resonance shift onCH=CH 1H-DOPC line in function of GM1concentration.1H-NMR spectroscopy has been used [1] toinvestigate the formation of ganglioside GM1 clustersin DOPC liposome bilayer. The 1H-DOPC NMR spectrashow that the presence of GM1 mo<strong>di</strong>fies someresonance lines (fig. 1). These mo<strong>di</strong>fications areimputable to the interaction of DOPC with GM1.Above a certain GM1 concentration the trend of such<strong>di</strong>stortions suggests the formation of GM1aggregates. Our work provides a new and simpleNMR proof of the GM1 clustering in DOPC liposomesand therefore on model cell membranes; it allows toestimate the mean size of GM1 aggregates and theGM1 concentration at which clustering starts. Inad<strong>di</strong>tion, NMR-PFG self-<strong>di</strong>ffusion coefficientmeasurements have enable us to confirm and extendthe chemical shift results. Thanks to our approachthe influence of cluster formation on the generalorganization of the DOPC bilayer has been shown. Inparticular its local <strong>di</strong>sordering effect on DOPC-DOPCinteractions has been proven. More over, cluster ra<strong>di</strong>iTwo binary aqueous mixtures which contain thesmall amphiphilic molecules TMAO (trimethylamine-N-oxide) and TBA (tert-butyl alcohol) have beeninvestigated by molecular dynamics simulations andNMR chemical shift and self-<strong>di</strong>ffusion measurements.TMAO is an osmolyte, while TBA is a monohydratealcohol. Both possess bulky hydrophobic groups andpolar heads, namely, NO in TMAO and OH in TBA.The hydrophilic/hydrophobic content of theseisosteric molecules strongly modulates the structureand dynamics of the hydration shell, which isthought to be responsible for the effects observed onproteins and phospholipids. Simulation results,especially on hydrogen-bond networking, spatialcorrelations, and self-<strong>di</strong>ffusivity, are consistent withNMR data and agree well with previous numericalstu<strong>di</strong>es on similar solutions. The methods employedallow the elucidation of the microscopic features ofthe solutions. For TBA solutions, the hydration shellis found to have a low density and a large spatialspread, and thus, above the molar fractionof 0.03,reduction of hydrophobic hydration drives selfaggregationof the solute. This effect does not takeplace in TMAO solutions, where the hydration shell ismore compact and stable, maintaining its structureover a wider range of solute concentrations.References[1] Sinibal<strong>di</strong> R., Casieri C., Melchionna S., Onori G.,Segre A.L., Viel S., Mannina L. and De Luca F., J.Phys. Chem. B, 110 (2006) 8885-8892.Authors:R. Sinibal<strong>di</strong> (b), C. Casieri (a,c) and F. De Luca (a,b).(a) CRS SOFT-INFM-CNR, Roma, Italy(b) Dip. <strong>di</strong> <strong>Fisica</strong>, Univ. <strong>di</strong> Roma La <strong>Sapienza</strong>, Roma,I(c) Dip. <strong>di</strong> <strong>Fisica</strong>, Università <strong>di</strong> L’Aquila, L’Aquila, I97SOFT Scientific <strong>Report</strong> 2004-06
Scientific <strong>Report</strong> – Self Assembly, Clustering, Structural arrestNon-invasive 1 H-NMR in porous materials of artistic interestNuclear Magnetic Resonance of 1 H-nuclei of waterconfined in porous me<strong>di</strong>a has become anirreplaceable tool for quantitative characterization ofthe structure of porous me<strong>di</strong>a. Proton relaxationexperiments allows evaluation of the equilibriumnuclear magnetization and extraction of <strong>di</strong>stributionsfunctions of the relaxation times (T 1 and T 2), whichin fully water saturated con<strong>di</strong>tion may be interprete<strong>di</strong>n terms of porosity and “pore-size” <strong>di</strong>stributions,respectively. The ability to use water molecules toexplore the pore space makes NMR methodsespecially appropriate for studying materials ofCultural Heritage interest. In fact, porous materials(i.e. concrete, mortar, stone, wood) can absorb orrelease water in response to thermo-hygrometricenvironmental mo<strong>di</strong>fications and their properties aregreatly affected by moisture content. Moreover,trapped water can <strong>di</strong>ssolve the components ofporous me<strong>di</strong>a, altering their porosity andtransporting air pollutants inside the pore space,causing corrosion and micro-fractures. Therefore, theknowledge of capillary properties and porosity ofartworks materials is essential for the evaluation ofthe conservation state and suitable non-destructive<strong>di</strong>agnostic techniques are required. Recently, all theNMR capability of studying porous systems hasbecome available for Cultural Heritage applications,thanks to the development of portable surfaceprobes such as the mq-ProFiler. Various are thetopics concerning the field of science for CulturalHeritage explored by single-sided NMR, some ofwhich are reported in the following.Determination of moisture fraction in wood. Themobile NMR probe has been used as a non-invasivetool for water content analysis on wood samples. Theporosity index, expressed as the fraction of thesensitivity volume of the probe occupied by waterhas been proposed as an alternative to moisturecontent index, namely the amount of water masswith respect to the mass of dried sample. In principlethe method can be applied to any kind of porousme<strong>di</strong>a that has no detectable proton signal from therigid matrix as, for instance, in buil<strong>di</strong>ng materials. Inwood, where proton signal can be detected also fromcellulose or other macromolecular components, someconsiderations and artifices have been proposed foreliminating this contribution. This method hasallowed performing moisture volume fraction analysison wood samples characterized by <strong>di</strong>fferent woodspecies, cutting and moisture content. The NMR datahave succesfully been compared with those obtainedby the gravimetric method.References[1] Casieri C., Senni L., Romagnoli M., SantamariaU., De Luca F., J. M. R., 171 (2004) 363-372.[2] Casieri C., Senni L., Romagnoli M., SantamariaU., De Luca F., in 8th Int. Conf. on “Non-destructiveTesting and Microanalysis for the Conservation of theCultural and Environmental Heritage”, 15-19 May2005, Lecce. ISBN 88-89758-00-7.AuthorsL. Senni (a,b), C. Casieri (a,c) and F. De Luca (a,b).NMR evaluation of hydrophobic treatments forstone conservation. The aim of this experimentwas to check the ability of NMR methods toquantitatively follow the absorption phenomenonunder <strong>di</strong>fferent wettability con<strong>di</strong>tions of the internalpore surfaces in “Lecce Stone”. A hydrophobicpolymer (PB72) has been applied through one face ofeach sample and relaxation data have been takenover the course of time without interrupting theabsorption process, simply by keeping the portabledevice on the surface opposite to the absorption. Themain experimental evidence was that for a sampletreated with a high amount of PB72 (478 mg in 3%(w/w) chloroform solution) when the absorption faceis the untreated one (Fig. 1a) initially the capillaryrise of water is reduced by the hydrophobic productand limited to smaller pores or to larger ones onlypartially filled with water. However, after the firsthours of absorption, the water molecules find a waythrough the polymeric barrier and invade all the porespace available at normal pressure con<strong>di</strong>tions.Instead, when the absorption face is the treated one(Fig 1b), the signal density <strong>di</strong>stributions are limitedto only the region of smaller T 2 for every absorptiontime, in<strong>di</strong>cating that the larger pores throughoutmuch of the sample have become somewhat waterrepellent.The results have been confirmed byMagnetic Resonance Imaging analysis, showing thatthe single-sided technique is a powerful tool for insitu evaluation of water-repellent treatments usedfor consolidation and/or protection of stone artifacts.(a)(b)Fig. 1: Water uptake kinetics in 2D visualization forthe time evolution of the T 2 <strong>di</strong>stribution through theuntreated face (a) and measurement from thetreated one (b) for the treated sample.References[1] Bortolotti V., Camaiti M., Casieri C., De Luca F.,Fantazzini P., Terenzi C., JMR, 181 (2006) 287-295.[2] Camaiti M., Casieri C., De Luca F., Fantazzini P.,Terenzi C., Stu<strong>di</strong>es in Conservation, (2007).[3] Casieri C., De Luca F., Fantazzini P., J. Appl.Phys. 97(4) 043901 (2005) 1-10.Authors:C. Terenzi (a,b), C. Casieri (a,c) and F. De Luca(a,b).(a) CRS SOFT-INFM-CNR, Roma, Italy(b) Dip. <strong>di</strong> <strong>Fisica</strong>, Univ. <strong>di</strong> Roma La <strong>Sapienza</strong>, Roma,I(c) Dip. <strong>di</strong> <strong>Fisica</strong>, Università <strong>di</strong> L’Aquila, L’Aquila, ISOFT Scientific <strong>Report</strong> 2004-0698
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