PMID- 26864080
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20160826
LR  - 20160225
IS  - 2040-3372 (Electronic)
IS  - 2040-3364 (Linking)
VI  - 8
IP  - 9
DP  - 2016 Mar 7
TI  - Dynamics of intramolecular spin exchange interaction of a nitronyl nitroxide 
      diradical in solution and on surfaces.
PG  - 5049-58
LID - 10.1039/c5nr08824k [doi]
AB  - In this paper we report the study of the dynamics of a thermally modulated 
      intramolecular spin exchange interaction of a novel diradical nitronyl 
      nitroxide-substituted disulfide in solution and when it is grafted on a gold 
      surface. The structure of this diradical was designed to have flexible chains 
      leading to intramolecular collisions and hence spin exchange interaction, and 
      with an appropriate binding group to be grafted on the gold surface to study its 
      behavior on the surface. In solution, this diradical shows a strong spin exchange 
      interaction between both radicals which is modulated by temperature, but also 
      gold nanoparticles (AuNPs) functionalized with this diradical permit 
      investigation of such a phenomenon in surface-grafted radicals. The spin-labelled 
      AuNP synthesis was optimized to obtain high coverage of spin labels to lead to 
      high spin exchange interaction. The obtained AuNPs were studied by Electron 
      Paramagnetic Resonance (EPR), UV-Vis, and IR spectroscopies, HR-TEM microscopy, 
      Cyclic Voltammetry (CV), Energy Dispersive X-ray analysis (EDX) and 
      Thermogravimetric Analysis (TGA). This inorganic-organic hybrid material also 
      showed dipolar interactions between its radicals which were confirmed by the 
      appearance in the EPR spectra of an |Deltams| = 2 transition at half-field. This 
      signal gives direct evidence of the presence of a high-spin state and permitted 
      us to study the nature of the magnetic coupling between the spins which was found 
      to be antiferromagnetic. Self-Assembled Monolayers (SAMs) of these radicals on 
      the Au (111) substrate were also prepared and studied by contact angle, X-Ray 
      Photoelectron Spectroscopy (XPS), Time-of-Flight Secondary Ion Mass Spectrometry 
      (ToF-SIMS), Cyclic Voltammetry and EPR. The magnetic as well as the 
      electrochemical properties of the hybrid surfaces were studied and compared with 
      the properties of this diradical in solution. Analogies between the properties of 
      AuNPs with high coverage of radicals and those of SAM were observed.
FAU - Lloveras, V
AU  - Lloveras V
AD  - Institut de Ciencia de Materials de Barcelona ICMAB (CSIC), Campus UAB, 08193 
      Bellaterra, Barcelona, Spain. j.vidal@icmab.es and CIBER de Bioingenieria, 
      Biomateriales y Nanomedicina (CIBER-BBN), Barcelona, Spain.
FAU - Badetti, E
AU  - Badetti E
AD  - Institut de Ciencia de Materials de Barcelona ICMAB (CSIC), Campus UAB, 08193 
      Bellaterra, Barcelona, Spain. j.vidal@icmab.es and CIBER de Bioingenieria, 
      Biomateriales y Nanomedicina (CIBER-BBN), Barcelona, Spain.
FAU - Veciana, J
AU  - Veciana J
AD  - Institut de Ciencia de Materials de Barcelona ICMAB (CSIC), Campus UAB, 08193 
      Bellaterra, Barcelona, Spain. j.vidal@icmab.es and CIBER de Bioingenieria, 
      Biomateriales y Nanomedicina (CIBER-BBN), Barcelona, Spain.
FAU - Vidal-Gancedo, J
AU  - Vidal-Gancedo J
AD  - Institut de Ciencia de Materials de Barcelona ICMAB (CSIC), Campus UAB, 08193 
      Bellaterra, Barcelona, Spain. j.vidal@icmab.es and CIBER de Bioingenieria, 
      Biomateriales y Nanomedicina (CIBER-BBN), Barcelona, Spain.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
PL  - England
TA  - Nanoscale
JT  - Nanoscale
JID - 101525249
EDAT- 2016/02/13 06:00
MHDA- 2016/02/13 06:01
CRDT- 2016/02/12 06:00
PHST- 2016/02/12 06:00 [entrez]
PHST- 2016/02/13 06:00 [pubmed]
PHST- 2016/02/13 06:01 [medline]
AID - 10.1039/c5nr08824k [doi]
PST - ppublish
SO  - Nanoscale. 2016 Mar 7;8(9):5049-58. doi: 10.1039/c5nr08824k.