DFT study of [Pt(Cl)2L] complex (L = rubeanic acid) and its derived compounds with DNA purine bases

In this study, we present a systematic computational investigation on the electronic properties of cisplatin (cis-[Pt(Cl)2(NH3)2] (CP) and complex [Pt(Cl)2L] (1) (L = rubeanic acid) employing all-electron density functional theory. In detail, we analyzed essential molecular properties such as geometrical parameters, ionization energies, electron affinity, highest occupied molecular orbital, and lowest unoccupied molecular orbital energies. Concerning CP, molecule 1 exhibited improved lipophilicity and a pronounced electrophilic property. Furthermore, to investigate and compare the DNA binding capability between CP and molecule 1, we extended the investigation to the guanine and adenine derived complexes, respectively. Complexes of molecule 1 with the adenine and guanine bases followed a similar trend of stability found for CP systems, with the highest affinity found for guanine complexes. Altogether, molecule 1 displayed promising physicochemical and druglikeness features to serve as a starting point for developing a drug-like enough that could be therapeutically useful

Performance of Different Atrial Conduction Velocity Estimation Algorithms Improves with Knowledge about the Depolarization Pattern

Quantifying the atrial conduction velocity (CV) reveals important information for targeting critical arrhythmia sites that initiate and sustain abnormal electrical pathways, e.g. during atrial flutter. The knowledge about the local CV distribution on the atrial surface thus enhances clinical catheter ablation procedures by localizing pathological propagation paths to be eliminated during the intervention. Several algorithms have been proposed for estimating the CV. All of them are solely based on the local activation times calculated from electroanatomical mapping data. They deliver false values for the CV if applied to regions near scars or wave collisions. We propose an extension to all approaches by including a distinct preprocessing step. Thereby, we first identify scars and wave front collisions and provide this information for the CV estimation algorithm. In addition, we provide reliable CV values even in the presence of noise. We compared the performance of the Triangulation, the Polynomial Fit and the Radial Basis Functions approach with and without the inclusion of the aforementioned preprocessing step. The evaluation was based on different activation patterns simulated on a 2D synthetic triangular mesh with different levels of noise added. The results of this study demonstrate that the accuracy of the estimated CV does improve when knowledge about the depolarization pattern is included. Over all investigated test cases, the reduction of the mean velocity error quantified to at least 25 mm/s for the Radial Basis Functions, 14 mm/s for the Polynomial Fit and 14 mm/s for the Triangulation approach compared to their respective implementations without the preprocessing step. Given the present results, this novel approach can contribute to a more accurate and reliable CV estimation in a clinical setting and thus improve the success of radio-frequency ablation to treat cardiac arrhythmias

Dye-sensitized Er3+-doped CaF2 nanoparticles for enhanced near-infrared emission at 1.5 μm

Lanthanide (Ln)-doped nanoparticles have shown potential for applications in various fields. However, the weak and narrow absorption bands of the Ln ions (Ln3+), hamper efficient optical pumping and severely limit the emission intensity. Dye sensitization is a promising way to boost the near-infrared (NIR) emission of Er3+, hence promoting possible application in optical amplification at 1.5 μm, a region that is much sought after for telecommunication technology. Herein, we introduce the fluorescein isothiocyanate (FITC) organic dye with large absorption cross section as energy donor of small-sized (∼3.6 nm) Er3+-doped CaF2 nanoparticles. FITC molecules on the surface of CaF2 work as antennas to efficiently absorb light, and provide the indirect sensitization of Er3+ boosting its emission. In this paper, we employ photoluminescence and transient absorption spectroscopy, as well as density functional theory calculations, to provide an in-depth investigation of the FITC → Er3+ energy transfer process. We show that an energy transfer efficiency of over 89% is achieved in CaF2:Er3+@FITC nanoparticles resulting in a 28 times enhancement of the Er3+ NIR emission with respect to bare CaF2:Er3+. Through the multidisciplinary approach used in our work, we are able to show that the reason for such high sensitization efficiency stems from the suitable size and geometry of the FITC dye with a localized transition dipole moment at a short distance from the surface of the nanoparticle

Nanoparticles in Cancer Diagnosis and Treatment

The use of tailored medication delivery in cancer treatment has the potential to increase efficacy while decreasing unfavourable side effects. For researchers looking to improve clinical outcomes, chemotherapy for cancer continues to be the most challenging topic. Cancer is one of the worst illnesses despite the limits of current cancer therapies. New anticancer medications are therefore required to treat cancer. Nanotechnology has revolutionized medical research with new and improved materials for biomedical applications, with a particular focus on therapy and diagnostics. In cancer research, the application of metal nanoparticles as substitute chemotherapy drugs is growing. Metals exhibit inherent or surface-induced anticancer properties, making metallic nanoparticles extremely useful. The development of metal nanoparticles is proceeding rapidly and in many directions, offering alternative therapeutic strategies and improving outcomes for many cancer treatments. This review aimed to present the most commonly used nanoparticles for cancer applications

Fabrication of nanoporous al by vapor-phase dealloying: Morphology features, mechanical properties and model predictions

The physical and chemical properties shown by nanoporous metals, related to their unique structure, make them very promising for application in several fields. Recently, vapor-phase dealloying has been reported as a method for the preparation of several non-noble nanoporous metals, alternatively to dealloying in aqueous solutions. Using this approach, we have successfully fabricated nanoporous Al starting from an Al20Zn80 nanocomposite obtained by ball milling. The nanocomposite was annealed at 550◦C under high-vacuum conditions, and the difference in the vapor pressures allowed the selective removal of Zn by vapor-phase dealloying. The morphology of the resulting nanoporous material was analyzed by Scanning Electron Microscopy showing pores from few to thousands of nm; moreover, the nanoporous 3D structure was observed through Serial Block Face-Scanning Electron Microscopy. A specific surface area as high as 73 m2 g−1 was estimated by N2 physisorption measurements. In addition, a fractal model able to well reproduce the morphology of nanoporous Al was built. This model has been used for predicting mechanical properties which are in good agreement with experimental data obtained by nanoindentation

Insight into the Properties of Heteroleptic Metal Dithiolenes: Multistimuli Responsive Luminescence, Chromism, and Nonlinear Optics

A comprehensive investigation of the functional properties of heteroleptic donor-M-acceptor dithiolene complexes Bu4N[MII(L1)(L2)] is presented (M = Pd, Pt). The acceptor L1 consists of the chiral (R)-(+)α-methylbenzyldithiooxamidate ((R)-α-MBAdto), the donor L2 is 2-thioxo-1,3-dithiole-4,5-dithiolato (dmit) in 1 (Pd) and 2 (Pt), 1,2-dicarbomethoxyethylenedithiolate (ddmet) in 3 (Pd) and 4 (Pt), or [4′,5′:5,6][1,4]dithiino[2,3-b]quinoxaline-1′,3′-dithiolato (quinoxdt) in 5 (Pd) and 6 (Pt). L1 is capable of undergoing proton exchange and promoting crystal formation in noncentrosymmetric space groups. L2 has different molecular structures while it maintains similar electron-donating capabilities. Thanks to the synergy of the ligands, 1-6 behave as H+ and Ag+ switchable linear chromophores. Moreover, the compounds exhibit a H+-switchable second-order NLO response in solution, which is maintained in the bulk for 1, 3, and 4 when they are embedded into a PMMA poled matrix. 5 and 6 show unique anti-Kasha H+ and Ag+ tunable colored emission originating from the quinoxdt ligand. A correlation between the electronic structure and properties is shown through density functional theory (DFT) and time-dependent DFT calculations

Anti-Kasha Conformational Photoisomerization of a Heteroleptic Dithiolene Metal Complex Revealed by Ultrafast Spectroscopy

We investigated the anti-Kasha photochemistry and anti-Kasha emission of d8-metal donor-acceptor dithiolene with femtosecond UV-vis transient absorption spectroscopy and molecular modeling. Experimentally, we found a lifetime of 1.4 ps for higher excited states, which is exceptionally long when compared to typical values for internal conversion (IC) (10 s of fs or less). Consequently, a substantial emission originates from the second excited state. Molecular modeling suggests this to be a consequence of the spatially separated molecular orbitals of the first and second excited states, which gives a charge transfer character to the IC. More surprisingly, we found that the inherent flexibility of the molecule allows the metal complex to access different configurations depending on the photoexcited state. We believe that this unique manifestation of anti-Kasha photoinduced conformational isomerization is facilitated by the exceptionally long lifetime of the second excited state

Effect of fluorination on the crystal and electronic structure of organometallic cyclopentadienyl-phenylenediamino-cobalt complexes

The fluorinated half sandwich complex [CpCoLF] (Cp = cyclopentadiene; LF = o-perfluoro-phenylenediimine; 2F) shows a T-shaped geometry with the LF ligand coplanar with the metallocycle. The molecules are dimerized in a head-to-tail fashion and arranged in a herringbone manner in the crystal packing. The crystal structure of 2F is different from that of the corresponding hydrocarbon compound (2H). Moreover, the differences due to the presence of fluorine atoms are also highlighted by the analysis of the intermolecular contacts, which show that 2F exhibits several F⋯F contacts, as well as aromatic intra-dimer π … π interactions in addition to C–H … π and C–H⋯F contacts. No relevant π … π interactions are observed in the case of 2H. Hirshfeld Surface (HS) analysis also depicted well the differences in the solid state interactions between the different crystal structures. In particular, HS has been useful in highlighting the differences observed between the crystal structure of 2H obtained from Rietveld refinement and that measured on single crystal (2HP and 2HSCH, respectively). The effect of the fluorination on the electronic structure has been investigated also by CV measurements and Density Functional Theory calculations. Both are consistent with a lowering in energy of the molecular orbitals. Data Mining Force Field calculations clearly indicate that the 2HSCH structure is more stable than the 2HP one. These findings can be explained in terms of the energy of the intermolecular interactions. The enhanced stability of the fluorine substitute can be easily explained by the large number of strong interactions involving fluorine atoms

Assessing the response of ground-dwelling beetles communities to different land-uses in Mediterranea cork oak systems

In our study, we assessed the response of beetles communities at low taxonomical resolution to different Mediterranean cork oak land-use systems. Spatial variation of dung-beetles communities was also analyzed because of their potential role as ecological indicators in grazed areas