: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Nanostructures have attracted huge interest as a rapidly growing class of materials for many applications. Several techniques have been used to characterize the size, crystal structure, elemental composition and a variety of other physical properties of nanoparticles. In several cases, there are physical properties that can be evaluated by more than one technique. Different strengths and limitations of each technique complicate the choice of the most suitable method, while often a combinatorial characterization approach is needed. In addition, given that the significance of nanoparticles in basic research and applications is constantly increasing, it is necessary that researchers from separate fields overcome the challenges in the reproducible and reliable characterization of nanomaterials, after their synthesis and further process (e.g. annealing) stages. The principal objective of this review is to summarize the present knowledge on the use, advances, advantages and weaknesses of a large number of experimental techniques that are available for the characterization of nanoparticles. Different characterization techniques are classified according to the concept/group of the technique used, the information they can provide, or the materials that they are destined for. We describe the main characteristics of the techniques and their operation principles and we give various examples of their use, presenting them in a comparative mode, when possible, in relation to the property studied in each case.

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Characterization techniques for nanoparticles: comparison and complementarity upon studying nanoparticle properties

Multidentate unsymmetrically-substituted Schiff bases and their metal complexes: Synthesis, functional materials properties, and applications to catalysis

Fluorinated Natural Graphite Cathode for Rechargeable Ionic Liquid Based Aluminum–Ion Battery

The authors thank the FCT (Fundacao para a Ciencia e Tecnologia) for financial support under
the framework of the Strategic Funding UID/FIS/04650/2019 and projects PTDC/BTMMAT/28237/2017, PTDC/EMD-EMD/28159/2017 and PTDC/FIS-MAC/28157/2017. Funds provided by FCT in the framework of EuroNanoMed 2016 call, Project LungChek
ENMed/0049/2016 are also gratefully acknowledged. D.M.C, L.C.F and C.M.C also thanks to
the FCT for the grants SFRH/BPD/121526/2016, SFRH/BD/145345/2019 and
SFRH/BPD/112547/2015, respectively. PMM thanks to the ENMed_CQ_CF_04_2018 grant.
Finally, the authors acknowledge funding by the Spanish Ministry of Economy and
Competitiveness (MINECO) through the project MAT2016-76039-C4-3-R (AEI/FEDER, UE)
and from the Basque Government Industry and Education Departments under the ELKARTEK,
HAZITEK and PIBA (PIBA-2018-06) programs, respectively.

Ionic Liquid–Polymer Composites: A New Platform for Multifunctional Applications

Water effect on physicochemical properties of 1-butyl-3-methylimidazolium based ionic liquids with inorganic anions

Protic ionic liquids (PILs) composed of the triethylammonium cation with dihydrogen phosphite, tosylate, and trifluoroacetate anions were synthesized. All samples were salts with melting points below 100 °C and were characterized via NMR spectroscopy, attenuated total reflection (ATR) spectroscopy, differential scanning calorimetry (DSC), and thermogravimetry (TG). The electrochemical characteristics of each protic ionic liquid were obtained using a combination of impedance spectroscopy and cyclic voltammetry. Moreover, the influence of water on the thermal behavior and conductivity of triethylammonium tosylate is studied. A linear correlation between the temperatures of melting and crystallization is established for a number of PILs, including both derivatives of triethylamine with different acids reported in the literature and the newly synthesized PILs. The optimal combination of thermal characteristics and electroconductivity was observed for triethylammonium trifluoroacetate and tosylate.

Thermal behavior and electrochemistry of protic ionic liquids based on triethylamine with different acids

Triethylammonium-based protic ionic liquids with sulfonic acids: Phase behavior and electrochemistry

Seven organic salts of 1-butyl-3-methylimidazolium with anions Br−, BF4
 −, NO3
 −, SO4
 2−, HSO4
 −, SCN−, PO
 4
 3−
 were prepared. Structure of these compounds is elucidated and purity is confirmed. The products are characterized by melting point, thin layer chromatography, data of elemental analysis, cromatomass-, NMR and IR spectroscopy. All these compounds are ionic liquids, five are low temperature ones. Principal thermal characteristics are found that allow accounting for the phase behavior of the prepared compounds at their application. Existence of intramolecular and intermolecular interactions between the heterocyclic anion and inorganic cation in by means of the formation of hydrogen bond is established.

Preparation of 1-butyl-3-methylimidazolium salts and study of their phase behavior and intramolecular intractions

Self-assembly by donor–acceptor complex formation in the (2,3,7,8,12,18-hexamethyl,13,17-diethyl,5-(2-pyridyl)porphinato)cobalt(II) (CoIIP)–1′-N-methyl-2′-(pyridin-4-yl)pyrrolidino[3′,4′:1,2][60]fullerene (PyC60) system was studied using chemical thermodynamics/kinetics, UV-vis, IR, 1H NMR spectroscopy, amperometry and quantum chemical B3LYP-D3/6-31G(d,p) methods. The results revealed the formation of a supramolecular 1 : 2 triad between CoIIP and PyC60. The equilibrium/rate constants of the donor–acceptor triad formation are observed to be (1.04 ± 0.12) × 1010 L2 mol−2 and (63.7 ± 4.5) mol−1 L s−1, respectively. The numerical values of these equilibrium/rate constants demonstrate a strong bonding between the CoIIP and fulleropyrrolidine moieties. The triad LUMO energy levels are predominantly spread on the C60 unit. However, the HOMO energy levels are mainly spread on the porphyrin ring pointing at the property of photoinduced electron transfer (PET) in the obtained triad. Modification of the covered natural oxide film titanium electrode surface in the voltammetry experiment was carried out by using the porphyrin–fullerene triad and the self-assembly components. The maximum efficiency coefficient of the incident photon energy conversion to current (IPCE) and photocurrent density values of (PyC60)2CoIIP at 365 nm are significantly larger than those of CoIIP and PyC60. The results are of interest for creating porphyrin-based donor–acceptor systems as components in organic photovoltaics.

Matvey S. Gruzdev

Papers

Water effect on physicochemical properties of 1-butyl-3-methylimidazolium based ionic liquids with inorganic anions

Thermal behavior and electrochemistry of protic ionic liquids based on triethylamine with different acids

Triethylammonium-based protic ionic liquids with sulfonic acids: Phase behavior and electrochemistry

Preparation of 1-butyl-3-methylimidazolium salts and study of their phase behavior and intramolecular intractions

Self-assembled cobalt(II)porphyrin–fulleropyrrolidine triads via axial coordination with photoinduced electron transfer