1. Spin transition in arrays of gold nanoparticles and spin crossover molecules
Edwin J Devid, Paulo N Martinho, M Venkata Kamalakar, Ivan Šalitroš, Úna Prendergast, Jean-François Dayen, Velimir Meded, Tibebe Lemma, Rodrigo González-Prieto, Ferdinand Evers, Tia E Keyes, Mario Ruben, Bernard Doudin, Sense Jan van der Molen ACS Nano. 2015 Apr 28;9(4):4496-507.doi: 10.1021/acsnano.5b01103.Epub 2015 Apr 13.
We investigate if the functionality of spin crossover molecules is preserved when they are assembled into an interfacial device structure. Specifically, we prepare and investigate gold nanoparticle arrays, into which room-temperature spin crossover molecules are introduced, more precisely, [Fe(AcS-BPP)2](ClO4)2, where AcS-BPP = (S)-(4-{[2,6-(dipyrazol-1-yl)pyrid-4-yl]ethynyl}phenyl)ethanethioate (in short, Fe(S-BPP)2). We combine three complementary experiments to characterize the molecule-nanoparticle structure in detail. Temperature-dependent Raman measurements provide direct evidence for a (partial) spin transition in the Fe(S-BPP)2-based arrays. This transition is qualitatively confirmed by magnetization measurements. Finally, charge transport measurements on the Fe(S-BPP)2-gold nanoparticle devices reveal a minimum in device resistance versus temperature, R(T), curves around 260-290 K. This is in contrast to similar networks containing passive molecules only that show monotonically decreasing R(T) characteristics. Backed by density functional theory calculations on single molecular conductance values for both spin states, we propose to relate the resistance minimum in R(T) to a spin transition under the hypothesis that (1) the molecular resistance of the high spin state is larger than that of the low spin state and (2) transport in the array is governed by a percolation model.
2. New porphyrin photosensitizers-Synthesis, singlet oxygen yield, photophysical properties and application in PDT
Xiaorong Wang, Hui Lv, Yingkai Sun, Guoping Zu, Xiaozhen Zhang, Yufang Song, Fengyang Zhao, Jingang Wang Spectrochim Acta A Mol Biomol Spectrosc. 2022 Oct 15;279:121447.doi: 10.1016/j.saa.2022.121447.Epub 2022 May 30.
This research on porphyrin-based photosensitizer system has a very important theoretical and practical significance in the photodynamic therapy (PDT) treatment of cancer. Based on this, in this article, a series of porphyrin derivatives were first designed and synthesized, and a "push-pull" porphyrin photosensitizer with two symmetrical ethanethioate groups was finally constructed. Based on the characterization of their chemical structures (1H and13C NMR, MS, IR, and UV-Vis spectroscopy) and the use of the density functional theory (DFT) and time-dependent DFT (TDDFT) to address the nature of the excited states as well as the dark/phototoxicity, the results have indicated the relationship between the porphyrin structure and properties. The experimental and theoretical UV-Vis absorption properties of porphyrins were discussed. The four porphyrin compounds synthesized all demonstrated a high capacity to generate singlet oxygen under long-wavelength (590 nm) light and low dark toxicity. Compared with the conventional porphyrin photosensitizers, P4 with a CT band (from 580 to 750 nm) is beneficial to the penetration of the light, presenting the potential for applications in PDT.
3. Electrochemistry of Tetrathiafulvalene Ligands Assembled on the Surface of Gold Nanoparticles
Jiří Janoušek, Jiří Rybáček, Miloš Buděšínský, Lubomír Pospíšil, Irena G Stará, Ivo Starý Molecules. 2022 Nov 7;27(21):7639.doi: 10.3390/molecules27217639.
The synthesis of a tetrathiafulvalene (TTF) derivative, S-[4-({4-[(2,2'-bi-1,3-dithiol-4-ylmethoxy)methyl] phenyl}ethynyl)phenyl] ethanethioate, suitable for the modification of gold nanoparticles (AuNPs), is described in this article. The TTF ligand was self-assembled on the AuNP surface through ligand exchange, starting from dodecanethiol-stabilized AuNPs. The resulting modified AuNPs were characterized by TEM, UV-Vis spectroscopy, and electrochemistry. The most suitable electrochemical method was the phase-sensitive AC voltammetry at very low frequencies of the sine-wave perturbation. The results indicate a diminishing electronic communication between the two equivalent redox centers of TTF and also intermolecular donor-acceptor interactions manifested by an additional oxidation wave upon attachment of the ligand to AuNPs.