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1.
Chemistry ; 20(19): 5555-8, 2014 May 05.
Artigo em Inglês | MEDLINE | ID: mdl-24604877

RESUMO

The absolute configuration of (R,R)-2,3-dideuterooxirane, which has been independently determined using Coulomb explosion imaging, has been unambiguously chemically correlated with the stereochemical key reference (+)-glyceraldehyde. This puts the absolute configuration of D(+)-glyceraldehyde on firm experimental grounds.

2.
Nano Lett ; 11(11): 4652-5, 2011 Nov 09.
Artigo em Inglês | MEDLINE | ID: mdl-21961931

RESUMO

Spin-based properties, applications, and devices are commonly related to magnetic effects and to magnetic materials. Most of the development in spintronics is currently based on inorganic materials. Despite the fact that the magnetoresistance effect has been observed in organic materials, until now spin selectivity of organic based spintronics devices originated from an inorganic ferromagnetic electrode and was not determined by the organic molecules themselves. Here we show that conduction through double-stranded DNA oligomers is spin selective, demonstrating a true organic spin filter. The selectivity exceeds that of any known system at room temperature. The spin dependent resistivity indicates that the effect cannot result solely from the atomic spin-orbit coupling and must relate to a special property resulting from the chirality symmetry. The results may reflect on the importance of spin in determining electron transfer rates through biological systems.


Assuntos
DNA/química , DNA/ultraestrutura , Modelos Químicos , Simulação por Computador , Condutividade Elétrica , Elétrons
3.
Top Curr Chem ; 298: 237-57, 2011.
Artigo em Inglês | MEDLINE | ID: mdl-21321804

RESUMO

Self-assembled monolayers (SAMs) of organic dipolar molecules have new electronic and magnetic properties that result from their organization, despite the relatively weak interaction among the molecules themselves. Here we review the origin of this cooperative effect and summarize results obtained on spin selective electron transmission through such monolayers that are made from chiral molecules. We show that SAMs containing chiral dipolar molecules behave like magnetic layers which may serve as spin filters, even without applying an external magnetic field to the layer.


Assuntos
Elétrons , Estereoisomerismo , DNA/química , Magnetismo , Peptídeos/química
4.
Science ; 342(6162): 1084-6, 2013 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-24288330

RESUMO

In chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples. Determining absolute configurations of chiral molecules in the gas phase is still a formidable challenge. Here we demonstrate the determination of the absolute configuration of isotopically labeled (R,R)-2,3-dideuterooxirane by foil-induced Coulomb explosion imaging of individual molecules. Our technique provides unambiguous and direct access to the absolute configuration of small gas-phase species, including ions and molecular fragments.


Assuntos
Óxido de Etileno/química , Imagem Molecular/métodos , Deutério , Fenômenos Eletromagnéticos , Gases , Marcação por Isótopo , Conformação Molecular , Estereoisomerismo
6.
Phys Chem Chem Phys ; 8(19): 2217-24, 2006 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-16688303

RESUMO

New electronic and magnetic properties are induced by the adsorption of closed packed monolayers on solid substrates. For many thiolated molecules self-assembled on gold, a surprisingly large paramagnetism is observed. In the case where the layers are made from chiral molecules, in addition an unexpectedly large electronic dichroism is observed, which manifests itself as spin specific electron transmission. This dichroism was observed for monolayers made from polyalanine and from DNA. Self-assembled monolayers of double-stranded DNA oligomers on gold interact with polarized electrons similarly to a strong and oriented magnetic field. The direction of the field for right-handed DNA is away from the substrate. Moreover, the layer shows very high paramagnetic susceptibility. Interestingly, thiolated single-stranded DNA oligomers on gold do not show this effect. All the observations can be rationalized by assuming organization induced charge transfer between the substrate and the organic layer. The charge transfer results in spin alignment of the transferred electrons/holes. While for achiral molecules the spin alignment varies among the domains, in the case of monolayer made from chiral molecules the alignment is the same across the entire sample. When magnetic field is applied, large magnetic moment is observed that results from orbital magnetism.


Assuntos
Cristalização/métodos , DNA/química , DNA/ultraestrutura , Magnetismo , Nanoestruturas/química , Nanoestruturas/ultraestrutura , Compostos Orgânicos/química , Adsorção , Condutividade Elétrica , Eletrônica , Teste de Materiais
7.
Acc Chem Res ; 36(5): 291-9, 2003 May.
Artigo em Inglês | MEDLINE | ID: mdl-12755638

RESUMO

Low-energy electron photoemission spectroscopy (LEPS) allows the study of the electronic properties of organized organic thin films (OOTF) adsorbed on conducting surfaces by monitoring the energy and angular distribution of electrons emitted from the substrate and transmitted through the film. The transmission properties are explained by electronic band structure in the organic film. This band is an example of an electron resonance that is delocalized in the layer. It results from the two-dimensional nature of the layer. Other resonances in the transmission spectra are also discussed, as well as their experimental manifestation. The temperature dependence of the electron transmission efficiency is explained in terms of dependence of the transmission probability on the initial momentum of the electron and on the relative orientation of the electron velocity and the molecules in the film. Hence, despite the fact that the molecules in the OOTF are weakly interacting, when not charged, the electron transmission through the film is governed by cooperative effects. These effects must be taken into account when considering electronic properties of adsorbed layers.

8.
Phys Rev Lett ; 92(8): 087205, 2004 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-14995811

RESUMO

Recently, unusual giant magnetic properties were found experimentally in some organized organic monolayers adsorbed on solid substrates. A model is presented which explains the observed phenomenon. The model is based on the special properties of electrons transferred from the substrate to the layer as a result of the adsorption process. Triplet pairing of those electrons is forced by the special 2D properties of the organic layer. Such pairs are confined within domains in the organic layer and their quantum statistics provide a model that explains the unique magnetization as well as all other features of the experimental observations. The model suggests the possible existence of Bose-Einstein condensation at room temperature on the scale of the domains.

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