RESUMEN

Systematic structure prediction of LinPm nanoclusters was performed for a wide range of compositions (0 ≤ n ≤ 10, 0 ≤ m ≤ 20) using the evolutionary global optimization algorithm USPEX coupled with density functional calculations. With increasing Li concentration, the number of P-P bonds in the cluster reduces and the phosphorus backbone undergoes the following transformations: elongated tubular → multi-fragment (with mainly P5 rings and P7 cages) → cyclic topology → branched topology → P-P dumbbells → isolated P ions. By applying several stability criteria, we determined the most favorable LinPm clusters and found that they are located in the compositional area between m ≈ n/3 and m ≈ n/3 + 6. For instance, the Li3P7 cluster has the highest stability and is known to be the structural basis of the corresponding bulk crystal. The obtained results provide valuable insights into the lithiation mechanism of nanoscale phosphorus which is of interest for development of novel phosphorus-based anode materials.

RESUMEN

Systematic structure prediction of CunAum nanoclusters was carried out for a wide compositional area (n + m ≤ 15) using the evolutionary algorithm USPEX and DFT calculations. The obtained structural data allowed us to assess the local stability of clusters and their suitability for catalysis of CO oxidation. Using these two criteria, we selected several most promising clusters for an accurate study of their catalytic properties. The adsorption energies of reagents, reaction paths, and activation energies were calculated. We found several cases with low activation energies and explained these cases using the patterns of structural change at the moment of CO2 desorption. The unique case is the Cu7Au6 cluster, which has extremely low activation energies for all transition states (below 0.05 eV). We thus showed that higher flexibility due to the binary nature of nanoclusters makes it possible to achieve the maximum catalytic activity. Considering the lower price of copper, Cu-Au nanoparticles are a promising new family of catalysts.

RESUMEN

Elemental phosphorus has a striking variety of allotropes, which we analyze by looking at stable phosphorus clusters. We determine the ground-state structures of Pn clusters in a wide range of compositions (n = 2-50) using density functional calculations and global optimization techniques. We explain why the high-energy white phosphorus is so easily formed, compared to the much more stable allotropes - the tetrahedral P4 cluster is so much more stable than nearby compositions that only by increasing the size to P10 one can get a more stable non-P4-based structure. Starting from 17 atoms, phosphorus clusters have a single-stranded structure, consisting of a set of well-resolved structural units connected by P2 linking fragments. The investigation of relative stability has revealed even-odd alternations and structural magic numbers. The former are caused by the higher stability of clusters with even numbers of atoms due to closed electronic shells. The structural magic numbers are associated with the presence of particular stable structural units and lead to enhanced stability of P18+12k (k = 0, 1, 2) clusters. We also compare the energies of the obtained ground-state structures with clusters of different phosphorus allotropes. Clusters of fibrous phosphorus are energetically the closest to the ground states, white phosphorus clusters are found to be less stable, and the least stable allotrope at the nanocluster scale is black phosphorene.

RESUMEN

Antibiotic resistance is a global threat and requires the search for new treatment strategies. Natural antimicrobial peptides (AMPs) have pronounced antibacterial, antiviral, antifungal, and antitumor activity. AMPs' clinical use is complicated by the high synthesis costs and rapid proteolytic degradation. The search for small molecules, inducers of endogenous AMP expression, could become a new approach. Here, we investigated for the first time the effect of seven small molecules (andrographolide, levofloxacin, azithromycin, montelukast, 4-phenylbutyric acid, rosuvastatin and valsartan) on AMP (beta-defensin-1, hBD-1 and cathelicidin, LL-37) serum levels in rats. In control groups, the level of hBD-1 was 295.0 (292.9-315.4) pg/mL, and for LL-37, it was 223.8 (213.3-233.6) pg/mL. Andrographolide (ANDR) and 4-phenylbutyric acid (4-PHBA) administration significantly enhanced the level of both AMPs. The hBD-1 level was 581.5 (476.3-607.7) pg/mL for ANDR and 436.9 (399.0-531.6) pg/mL for 4-PHBA. The LL-37 level was 415.4 (376.2-453.8) pg/mL for ANDR and 398.9 (355.7-410.1) pg/mL for 4-PHBA. Moreover, we have shown that these compounds reduce mortality in a murine model of sepsis caused by a carbapenem-resistant Klebsiella aerogenes isolate. From our point of view, these small molecules are promising candidates for further study as potent AMP inducers. The data obtained allow the development of new strategies to combat antibiotic resistance and infectious diseases.

RESUMEN

We address the question why among the multitude of imaginable CnHm compositions some are easily synthesizable and abundant in nature, while others are not. To shed light on this problem we borrow approaches from nanocluster study, where stability with respect to neighboring compositions is used as a criterion of "magic" (particularly stable) clusters. By merging this criterion with predictions of lowest-energy structures of all CnHm molecules in a wide range of compositions (n ≤ 20, m ≤ 42) we provide guidelines for predicting the presence or absence of certain hydrocarbon molecules in various environments, their relative abundance and reactivity/inertness. The resulting maps of stability show the increased stability of C2nH2 compounds, polyaromatic hydrocarbons, and diamondoids, which is supported by experimental studies of the interstellar medium, flames, and petroleum fractions. This approach can be applied to any other molecular system, rationalizing the diversity of known compounds and predicting new potentially synthesizable molecules.

RESUMEN

The search and development of new antibiotics is relevant due to widespread antibiotic resistance. One of the promising strategies is the de novo design of novel antimicrobial peptides. The amino acid sequences of 198 novel peptides were obtained using a generative long short-term memory recurrent neural network (LSTM RNN). To assess their antimicrobial effect, we synthesized five out of 198 generated peptides. The PEP-38 and PEP-137 peptides were active in vitro against carbapenem-resistant isolates of Klebsiella aerogenes and K. pneumoniae. PEP-137 was also active against Pseudomonas aeruginosa. The remaining three peptides (PEP-36, PEP-136 and PEP-174) showed no antibacterial effect. Then the effect of PEP-38 and PEP-137 (a single intraperitoneal administration of a 100 µg dose 30 min after infection) on animal survival in an experimental murine model of K. pneumoniae-induced sepsis was investigated. As a control, two groups of mice were used: one received sterile saline, and the other received inactive in vitro PEP-36 (a single 100 µg dose). The PEP-36 peptide was shown to provide the highest survival rate (66.7%). PEP-137 showed a survival rate of 50%. PEP-38 was found to be ineffective. The data obtained can be used to develop new antibacterial peptide drugs to combat antibiotic resistance.

RESUMEN

The absence of effective drugs for COVID-19 prevention and treatment requires the search for new candidates among approved medicines. Fundamental studies and clinical observations allow us to approach an understanding of the mechanisms of damage and protection from exposure to SARS-CoV-2, to identify possible points of application for pharmacological interventions. In this review we presented studies on the anti-inflammatory, antioxidant, and immunotropic properties of melatonin. We have attempted to present scientifically proven mechanisms of action for the potential therapeutic use of melatonin during SARS-CoV-2 infection. A wide range of pharmacological properties allows its inclusion as an effective addition to the methods of prevention and treatment of COVID-19.

RESUMEN

Molecular magnetism and specifically magnetic molecules have recently gained plenty of attention as key elements for quantum technologies, information processing, and spintronics. Transition to the nanoscale and implementation of ordered structures with defined parameters is crucial for advanced applications. Single-walled carbon nanotubes (SWCNTs) provide natural one-dimensional confinement that can be implemented for encapsulation, nanosynthesis, and polymerization of molecules into nanoribbons. Recently, the formation of atomically precise graphene nanoribbons inside SWCNTs has been reported. However, there have been only a limited amount of approaches to form ordered magnetic structures inside the nanotube channels and the creation of magnetic nanoribbons is still lacking. In this work we synthesize and reveal the properties of cobalt-phthalocyanine based nanoribbons (CoPcNRs) encapsulated in SWCNTs. Raman spectroscopy, transmission electron microscopy, absorption spectroscopy, and density functional theory calculations allowed us to confirm the encapsulation and to reveal the specific fingerprints of CoPcNRs. The magnetic properties were studied by transverse magnetooptical Kerr effect measurements, which indicated a strong difference in comparison with the pristine unfilled SWCNTs due to the impact of Co incorporated atoms. We anticipate that this approach of polymerization of encapsulated magnetic molecules inside SWCNTs will result in a diverse class of protected low-dimensional ordered magnetic materials for various applications.

RESUMEN

Silicon nanocrystals (NCs) have great potential for applications in optoelectronics, photovoltaics and biomedicine. The photo-physical characteristics of these particles strongly depend on whether they are crystalline or amorphous. This structural order is sensitive to the synthesis details. To understand the morphology of hydrogen-passivated silicon clusters and find how it depends on the passivation degree, we calculated the optimal structures of SinH2m clusters with n ≤ 21 and 2m ≤ 30. We found that as the hydrogen amount increases, clusters run through three structural types: (i) amorphous clusters with dangling bonds (DBs), (ii) amorphous clusters without DBs at intermediate passivation, and (iii) crystalline clusters. We describe a mechanism which removes dangling bonds in the amorphous clusters of the second type and shows its key importance for cluster structure formation. The crystalline lattice (diamond or lonsdaleite) is found to emerge when all broken bonds at the NC surface are passivated. We constructed the phase P-T diagram of Si-H clusters, compared it with the available experimental data and discussed the transfer of our results to large Si nanoparticles.

RESUMEN

Pd-Bi nanoparticles show high efficiency in catalyzing gluconic acid production by the glucose oxidation reaction. Although this type of catalyst was studied for some time, the correlation between bismuth content and catalytic activity is still unclear. Moreover, there is little information on the principles of the formation of Pd-Bi nanoparticles. In this work, the relation between bismuth content and the activity and selectivity of the PdxBiy/Al2O3 catalyst in the glucose oxidation process was studied. The catalytic samples were prepared by co-impregnation of the alumina support utilizing the metal-organic precursors of Pd and Bi. The samples obtained were tested in the glucose oxidation reaction and were studied by transmission electron microscopy (TEM), X-ray fluorescence analysis, X-ray photoelectron spectroscopy (XPS), and BET adsorption. It has been found that the Pd3 : Bi1 atomic ratio grants the highest catalytic efficiency for the studied samples. To explain this, we predicted stable Pd-Bi nanoparticles using ab initio evolutionary algorithm USPEX. The calculations demonstrate that nanoparticles tend to form Pd(core)-Bi(shell) structures turning to a crown-jewel morphology at lower Bi concentration, thus exposing the active Pd centers while maintaining the promoting effect of Bi.

RESUMEN

Constructing trap-free nanomaterials is a challenge that requires a fundamental understanding of the trapping phenomenon, especially the structural features responsible for electronic localization. Previously, such trapping configurations were explored by manual insertion of surface defects according to researchers' intuition, e.g. Cd-Se-Cd moiety [Houtepen et al., Chem. Mater., 2017, 29, 752]. In this study we report new types of traps in CdSe nanoclusters, including the metal-based one, which were found using a novel, unbiased approach. Namely, we screened a vast number of globally optimized CdnSem clusters (n,m ≤ 15) for localized electronic states. These systems model the wide diversity of defects in unpassivated areas of a nanocluster surface, while still being accessible for ab initio global optimization. Despite this variety, all 39 traps we found fall into 3 types, including two new ones. Such a reduction shows the universal character of discovered traps, irrelevant to the global structure of a cluster. Many of these traps not only have newly reported atomic arrangements, but also original confinement mechanisms which are explained at the atomistic level. We found that the relaxation and global optimization of the cluster structure greatly reduce the number of traps and push the trap energies from midgap to the near-gap edge positions, which agrees with the spectral measurements of II-VI semiconductor nanocrystals.

RESUMEN

The aims of this study were: (i) To investigate the activity of recombinant AMPs HNP-1 and hBD-1 in combination with cefotaxime against Staphylococcus aureus strains (MSSA and MRSA) in vitro using checkerboard method; (ii) To investigate the activity of HNP-1 and hBD-1 encapsulated in silicon nanoparticles (niosomes) in the treatment of MRSA-infected wound in rats. For this S. aureus strains (MSSA and MRSA) were isolated from patients with diabetic foot infection. Cefotaxime, recombinant HNP-1 and hBD-1 (in all possible combinations with each other) were used for testing by the checkerboard method. Two niosomal topical gels with HNP-1/hBD-1 were prepared to treat MRSA-infected wounds in rats. Gels were administered once a day, the control group-without treatment. Wound healing rate was calculated on the 4th, 9th and 16th days of the experiment and compared using one-way ANOVA with Bonferroni correction. MIC of HNP-1 for MSSA and MRSA was the same-1 mg/L. MIC of hBD-1 for MSSA and MRSA was also the same-0.5 mg/L. Topical gels with niosomal HNP-1 (or hBD-1) showed a significantly faster wound healing in comparison with the control. The data obtained open up prospects for use of AMPs encapsulated in silica nanoparticles for the development of new antibiotics.

Asunto(s)

Antibacterianos/farmacología , Infecciones Estafilocócicas/tratamiento farmacológico , alfa-Defensinas/farmacología , beta-Defensinas/farmacología , Administración Tópica , Animales , Antibacterianos/administración & dosificación , Cefotaxima/administración & dosificación , Cefotaxima/farmacología , Pie Diabético/tratamiento farmacológico , Pie Diabético/microbiología , Quimioterapia Combinada , Geles , Humanos , Masculino , Staphylococcus aureus Resistente a Meticilina/efectos de los fármacos , Staphylococcus aureus Resistente a Meticilina/aislamiento & purificación , Nanopartículas , Ratas , Ratas Wistar , Dióxido de Silicio/química , Infecciones Estafilocócicas/microbiología , Staphylococcus aureus/efectos de los fármacos , Staphylococcus aureus/aislamiento & purificación , Cicatrización de Heridas/efectos de los fármacos , alfa-Defensinas/administración & dosificación , beta-Defensinas/administración & dosificación

RESUMEN

Crystalline silica (SiO2) is a major material used in many technologies, yet the exact surface structures of silica polymorphs are still mostly unknown. Here we perform a comprehensive study of surface reconstructions of α-cristobalite (001), α-quartz (001) and stishovite (110) and (100) using evolutionary algorithm USPEX in conjunction with ab initio calculations. We found the well-known "dense surface" to be among low-energy reconstructions of α-quartz (001), as well as its previously proposed distorted version, which we call "shifted surface". For cristobalite and stishovite we show the formation of reconstructions without dangling bonds which share common features with well-known "dense surface" of α-quartz (001). We call them "dense cristobalite" and "dense stishovite" - all of these have honeycomb arrangements of corner-sharing SiO4-tetrahedra in the surface layers. These tetrahedral honeycombs have very low surface energies, and such tetrahedral surface pattern is observed even in stishovite (the bulk structure of which has SiO6-octahedra, rather than SiO4-tetrahedra).

RESUMEN

Oxidation of silicon nanoclusters depending on the temperature and oxygen pressure is explored from first principles using the evolutionary algorithm, and structural and thermodynamic analysis. From our calculations of 90 SinOm clusters we found that under normal conditions oxidation does not stop at the stoichiometric SiO2 composition, as it does in bulk silicon, but goes further placing extra oxygen atoms on the cluster surface. These extra atoms are responsible for light emission, relevant to reactive oxygen species and many of them are magnetic. We argue that the super-oxidation effect is size-independent and discuss its relevance to nanotechnology and miscellaneous applications, including biomedical ones.