Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 46
Filtrar
Mais filtros








Base de dados
Intervalo de ano de publicação
1.
Astrobiology ; 24(7): 698-709, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-39023275

RESUMO

Europa and Enceladus are key targets to search for evidence of life in our solar system. However, the surface and shallow subsurface of both airless icy moons are constantly bombarded by ionizing radiation that could degrade chemical biosignatures. Therefore, sampling of icy surfaces in future life detection missions to Europa and Enceladus requires a clear understanding of the necessary ice depth where unaltered organic biomolecules might be present. We conducted radiolysis experiments by exposing individual amino acids in ices and amino acids from dead microorganisms in ices to gamma radiation to simulate conditions on these icy worlds. In the pure amino acid samples, glycine did not show a detectable decrease in abundance, whereas the abundance of isovaline decreased by 40% after 4 MGy of exposure. Amino acids in dead Escherichia coli (E. coli) organic matter exhibited a gradual decline in abundances with the increase of exposure dosage, although at much slower rates than individual amino acids. The majority of amino acids in dead A. woodii samples demonstrated a step function decline as opposed to a gradual decline. After the initial drop in abundance with 1 MGy of exposure, those amino acids did not display further decreases in abundance after exposure up to 4 MGy. New radiolysis constants for isolated amino acids and amino acids in dead E. coli material for Europa/Enceladus-like conditions have been derived. Slow rates of amino acid destruction in biological samples under Europa and Enceladus-like surface conditions bolster the case for future life detection measurements by Europa and Enceladus lander missions. Based on our measurements, the "safe" sampling depth on Europa is ∼20 cm at high latitudes of the trailing hemisphere in the area of little impact gardening. Subsurface sampling is not required for the detection of amino acids on Enceladus-these molecules will survive radiolysis at any location on the Enceladus surface. If the stability of amino acids observed in A. woodii organic materials is confirmed in other microorganisms, then the survival of amino acids from a potential biosphere in Europa ice would be significantly increased.


Assuntos
Aminoácidos , Escherichia coli , Exobiologia , Meio Ambiente Extraterreno , Raios gama , Gelo , Aminoácidos/análise , Meio Ambiente Extraterreno/química , Escherichia coli/efeitos da radiação , Exobiologia/métodos , Gelo/análise , Júpiter
2.
Dalton Trans ; 53(4): 1482-1491, 2024 Jan 23.
Artigo em Inglês | MEDLINE | ID: mdl-38131298

RESUMO

A series of monocapped cobalt(II) tris-pyrazoloximates was obtained through the template condensation of the corresponding pyrazoloxime, phenylboronic acid and a suitable cobalt(II) halogenide. Comparing 3-acetylpyrazoloxime versus its methine-containing homolog, the former produced cobalt(II) clathrochelates in substantially higher yields due to the electron donating effect of the methyl substituent, increasing the N-donor ability of its oxime group. Their less N-donor analog with the electron acceptor trifluoromethyl group did not form cobalt(II) complexes of this type. In all their solvent-free and solvent-containing crystals, the encapsulated cobalt(II) ion adopted a high-spin state, as gauged by the Co-N bond lengths of 2.112(4)-2.188(9) Å, and was located almost in the center of its CoN6-coordination polyhedron. Their CoN6-polyhedra had an almost ideal trigonal-prismatic (TP) geometry with distortion angles φ below 4°. This TP-like geometry was assisted by hydrogen bonding between their NH groups and the apical counterion. The absence of methyl groups makes them close to an ideal TP. In contrast, stronger N-H⋯Cl hydrogen bonds occurred in the methyl-containing complex, while the Co-N bond lengths stayed the same at 2.144(2) Å on average. In its solvates with benzene, chloroform and acetone, there is a clear tendency for φ to decrease from 2.7(3)° to 0.47(13)°. The comparable effects of the ribbed methyl substituents, the cross-linking counterion and the lattice solvent on their molecular geometry were observed; the larger the distortions from an ideal TP geometry, the stronger the hydrogen bonds to the corresponding apical halogenide anion. The analysis of the experimental AC- and DC-magnetometry data for their fine-crystalline samples suggests that the passing from the derivative of the methyl-substituted synthon to that of its methine-containing homolog caused a substantial decrease in the magnetic susceptibility value χT and an increase in the QTM contribution to the magnetic relaxation. The effect of a cross-linking halogenide counteranion on the Orbach remagnetization barrier is greater than that of the solvatomorphism of their crystals.

3.
Nat Commun ; 14(1): 4689, 2023 Aug 04.
Artigo em Inglês | MEDLINE | ID: mdl-37542069

RESUMO

We study the Mie-like scattering from an open subwavelength resonator made of a high-index dielectric material, when its parameters are tuned to the regime of interfering resonances. We uncover a novel mechanism of superscattering, closely linked to strong coupling of the resonant modes and described by the physics of bound states in the continuum (BICs). We demonstrate that the enhanced scattering occurs due to constructive interference described by the Friedrich-Wintgen mechanism of interfering resonances, allowing to push the scattering cross section of a multipole resonance beyond the currently established limit. We develop a general non-Hermitian model to describe interfering resonances of the quasi-normal modes, and study subwavelength dielectric nonspherical resonators exhibiting avoided crossing resonances associated with quasi-BIC states. We confirm our theoretical findings by a scattering experiment conducted in the microwave frequency range. Our results reveal a new strategy to boost scattering from non-Hermitian systems, suggesting important implications for metadevices.

4.
Phys Chem Chem Phys ; 25(29): 20042-20048, 2023 Jul 26.
Artigo em Inglês | MEDLINE | ID: mdl-37462080

RESUMO

An approach to the luminance increase of the europium-based OLED is proposed through the formation of the mixed-ligand complex. The introduction of two diverse anionic ligands around one europium ion forming a mixed-ligand complex is confirmed by powder X-ray diffraction, 1H and 19F NMR spectroscopy, MALDI MS spectroscopy, and luminescence spectroscopy. A decrease in the symmetry of the coordination environment leads to a 50% reduction of the lifetime of the excited state. The obtained OLEDs based on mixed ligand europium complexes are significantly superior in luminance to OLEDs based on individual complexes.

5.
Molecules ; 28(8)2023 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-37110601

RESUMO

Acid-base characteristics (acidity, pKa, and hydricity, ΔG°H- or kH-) of metal hydride complexes could be a helpful value for forecasting their activity in various catalytic reactions. Polarity of the M-H bond may change radically at the stage of formation of a non-covalent adduct with an acidic/basic partner. This stage is responsible for subsequent hydrogen ion (hydride or proton) transfer. Here, the reaction of tricarbonyl manganese hydrides mer,trans-[L2Mn(CO)3H] (1; L = P(OPh)3, 2; L = PPh3) and fac-[(L-L')Mn(CO)3H] (3, L-L' = Ph2PCH2PPh2 (dppm); 4, L-L' = Ph2PCH2-NHC) with organic bases and Lewis acid (B(C6F5)3) was explored by spectroscopic (IR, NMR) methods to find the conditions for the Mn-H bond repolarization. Complex 1, bearing phosphite ligands, features acidic properties (pKa 21.3) but can serve also as a hydride donor (ΔG≠298K = 19.8 kcal/mol). Complex 3 with pronounced hydride character can be deprotonated with KHMDS at the CH2-bridge position in THF and at the Mn-H position in MeCN. The kinetic hydricity of manganese complexes 1-4 increases in the order mer,trans-[(P(OPh)3)2Mn(CO)3H] (1) < mer,trans-[(PPh3)2Mn(CO)3H] (2) ≈ fac-[(dppm)Mn(CO)3H] (3) < fac-[(Ph2PCH2NHC)Mn(CO)3H] (4), corresponding to the gain of the phosphorus ligand electron-donor properties.

6.
Dalton Trans ; 52(12): 3884-3895, 2023 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-36877091

RESUMO

A multistep general synthetic strategy towards polytopic carboranyl-containing (semi)clathrochelate metal complexes, based on the template synthesis, transmetallation, amide condensation and 1,3-dipolar cycloaddition reactions, is developed. Their mono(semi)clathrochelate precursors with a single reactive group were obtained using a transmetallation of the triethylantimony-capped macrobicyclic precursor. The thus obtained carboxyl-terminated iron(II) semiclathrochelate underwent a macrobicyclization with zirconium(IV) phthalocyaninate to form the corresponding phthalocyaninatoclathrochelate. The direct one-pot template condensation of the suitable chelating and cross-linking ligand synthons on the Fe2+ ion as a matrix was also used for its preparation. Further amide condensation of the aforementioned semiclathrochelate and hybrid complexes with propargylamine in the presence of carbonyldiimidazole gave the (pseudo)cage derivatives with a terminal CC bond. Their "click" reaction with an appropriate carboranylmethyl azide afforded the ditopic carboranosemiclathrochelates and the tritopic carboranyl-containing phthalocyaninatoclathrochelates with a flexible spacer fragment between their polyhedral entities. The obtained new complexes were characterized using elemental analysis, MALDI-TOF mass spectrometry, multinuclear NMR, and UV-vis spectroscopy, and by single crystal X-ray diffraction experiments. Their FeN6-coordination polyhedra show a truncated trigonal-pyramidal geometry, while the cross-linking heptacoordinate Zr4+ or Hf4+ cations in the hybrid compounds form the MIVN4O3-coordination polyhedra with the geometry of a capped trigonal prism.

7.
Micromachines (Basel) ; 14(3)2023 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-36984998

RESUMO

The present study aimed to improve the optical sensing performance of tapered optical fiber sensors toward aqueous Rhodamine B solution of different concentrations by applying single-walled carbon nanotubes (SWCNTs). The functional coating was formed on the surface of the tapered optical fiber sensor using an aerosol layer-by-layer deposition method. Before deposition, the SWCNTs were processed with multistage liquid-phase treatment in order to form a stable dispersion. The effect of SWCNT treatment was investigated through Raman spectroscopy. The deposition of 220 layers caused a reduction of up to 60% of the initial optical power of radiation propagating through the optical fiber core. The optical fiber sensor coated with SWCNTs demonstrated significantly higher sensitivity compared to a non-coated sensor in the range of 2-32 mg/L of Rhodamine B concentration in an aqueous solution. The experimental results demonstrated that the sensitivity was increased 10 times from 32 (mg/L)-1, for the non-coated sensor, up to 317 (mg/L)-1 after SWCNT coating deposition. Moreover, the SWCNT-coated sensor demonstrated high repeatability that allowed for the evaluation of the concentration regardless of the previously analyzed dye concentration.

8.
Dalton Trans ; 52(10): 2928-2932, 2023 Mar 07.
Artigo em Inglês | MEDLINE | ID: mdl-36811361

RESUMO

The title cobalt(II) pseudoclathrochelate complexes possess an intermediate trigonal prismatic-trigonal antiprismatic geometry. As follows from PPMS data, they exhibit an SMM behaviour with Orbach relaxation barriers of approximately 90 K. Paramagnetic NMR experiments confirmed a persistence of these magnetic characteristics in solution. Therefore, a straightforward apical functionalization of this 3D molecular platform for its targeted delivery to a given biosystem can be performed without substantial changes.

9.
Dalton Trans ; 52(2): 347-359, 2023 Jan 03.
Artigo em Inglês | MEDLINE | ID: mdl-36511081

RESUMO

Fast crystallization of the monoclathrochelate cobalt(II) intracomplex [Co(Cl2Gm)3(BAd)2] (where Cl2Gm2- is a dichloroglyoxime dianion and BAd is an adamantylboron capping group, 1), initially obtained by the direct template condensation of the corresponding chelating α-dioximate and cross-linking ligand synthons on the Co2+ ion as a matrix, from benzene or dichloromethane afforded its structural triclinic and hexagonal polymorphs. Its prolonged recrystallization from dichloromethane under air atmosphere and sunlight irradiation unexpectedly gave the crystals of the CoIIICoIICoIII-trinuclear dodecachloro-bis-clathrochelate intracomplex [[CoIII(Cl2Gm)3(BAd)]2CoII] (2), the molecule of which consists of two macrobicyclic frameworks with encapsulated low-spin (LS) Co3+ ions, which are cross-linked by a µ3-bridging Co2+ ion as a bifunctional Lewis-acidic center. The most plausible pathway of such a 1 → 2 transformation is based on the photoinitiated radical oxidation of dichloromethane with air oxygen giving the reactive species. Cobalt(II) monoclathrochelate 1 was found to undergo a temperature-induced spin crossover (SCO) both in its solutions and in the solid state. In spite of the conformational rigidity of the corresponding quasiaromatic diboron-capped tris-α-dioximate framework, the main parameters of this SCO transition (i.e., its completeness and gradual character) are strongly affected by the nature of the used solvent (in the case of its solutions) and by the structural polymorphism of its crystals (in the solid state). In the latter case, the LS state (S = 1/2) of this complex is more thermally stable and, therefore, the cobalt(II)-centered 1/2 → 3/2 SCO is more gradual than that in solutions.

10.
Nanomaterials (Basel) ; 12(16)2022 Aug 16.
Artigo em Inglês | MEDLINE | ID: mdl-36014677

RESUMO

A technology for the formation and bonding with a substrate of hybrid carbon nanostructures from single-walled carbon nanotubes (SWCNT) and reduced graphene oxide (rGO) by laser radiation is proposed. Molecular dynamics modeling by the real-time time-dependent density functional tight-binding (TD-DFTB) method made it possible to reveal the mechanism of field emission centers formation in carbon nanostructures layers. Laser radiation stimulates the formation of graphene-nanotube covalent contacts and also induces a dipole moment of hybrid nanostructures, which ensures their orientation along the force lines of the radiation field. The main mechanical and emission characteristics of the formed hybrid nanostructures were determined. By Raman spectroscopy, the effect of laser radiation energy on the defectiveness of all types of layers formed from nanostructures was determined. Laser exposure increased the hardness of all samples more than twice. Maximum hardness was obtained for hybrid nanostructure with a buffer layer (bl) of rGO and the main layer of SWCNT-rGO(bl)-SWCNT and was 54.4 GPa. In addition, the adhesion of rGO to the substrate and electron transport between the substrate and rGO(bl)-SWCNT increased. The rGO(bl)-SWCNT cathode with an area of ~1 mm2 showed a field emission current density of 562 mA/cm2 and stability for 9 h at a current of 1 mA. The developed technology for the formation of hybrid nanostructures can be used both to create high-performance and stable field emission cathodes and in other applications where nanomaterials coating with good adhesion, strength, and electrical conductivity is required.

11.
Astrobiology ; 22(9): 1099-1115, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35749703

RESUMO

Amino acids are fundamental to life as we know them as the monomers of proteins and enzymes. They are also readily synthesized under a variety of plausible prebiotic conditions and are common in carbon-rich meteorites. Thus, they represent a reasonable class of organics to target in the search for prebiotic chemistry or chemical evidence of life on Mars. However, regardless of their origin, amino acids and other organic molecules present in near-surface regolith and rocks on Mars can be degraded by exposure to cosmic rays that can penetrate to a depth of a few meters. We exposed several pure amino acids in dry and hydrated silicate mixtures and in mixtures of silicates with perchlorate salts to gamma radiation at various temperatures and radiation doses representative of the martian near-subsurface. We found that irradiation of amino acids mixed with dry silica powder increased the rate of amino acid radiolysis, with the radiolysis constants of amino acids in silicate mixtures at least a factor of 10 larger compared with the radiolysis constants of amino acids alone. The addition of perchlorate salts to the silicate samples or hydration of silicate samples further accelerated the rate of amino acid destruction during irradiation and increased the radiolysis constants by a factor of ∼1.5. Our results suggest that even low-molecular-weight amino acids could degrade in just ∼20 million years in the top 10 cm of the martian surface regolith and rock, and even faster if the material contains elevated abundances of hydrated silicate minerals or perchlorates. We did not detect evidence of amino acid racemization after gamma radiation exposure of the samples, which indicates that the chirality of some surviving amino acids may still be preserved. Our experimental results suggest serious challenges for the search of ancient amino acids and other potential organic biosignatures in the top 2 m of the martian surface.


Assuntos
Meio Ambiente Extraterreno , Marte , Aminoácidos/química , Meio Ambiente Extraterreno/química , Sais , Silicatos
12.
Polymers (Basel) ; 14(4)2022 Feb 15.
Artigo em Inglês | MEDLINE | ID: mdl-35215656

RESUMO

Recycling of plastic waste, in particular polypropylene, represents one of the most pressing challenges facing humanity. Despite the promise of chemical methods for recycling polypropylene, they usually require a high temperature and are energy-intensive. In this work, we investigated the oxidative thermolysis of polypropylene in aqueous media. This approach rendered it possible to carry out the decomposition of the polymer at a comparatively low temperature (150 °C). It was shown that among the tested, the most promising aqueous medium for the decomposition of polypropylene is water saturated with gaseous oxygen at an elevated pressure (14 bar) and at a temperature of 150 °C. In such an environment, polypropylene was converted mostly to acetic acid (up to 1.3 g/g acetic acid to starting polypropylene mass ratio). Moreover, methanol, formic acid, and propionic acid were also detected as the products. Finally, the applicability of the proposed recycling method to real polypropylene waste was shown.

13.
Phys Chem Chem Phys ; 24(2): 1167-1173, 2022 Jan 04.
Artigo em Inglês | MEDLINE | ID: mdl-34931208

RESUMO

A recently introduced concept of reduced paramagnetic shifts (RPS) in NMR spectroscopy is applied here to a series of paramagnetic complexes with different metal ions, such as iron(II), iron(III) and cobalt(II), in different coordination environments of N-donor ligands, including a unique trigonal-prismatic geometry that is behind some record single-molecule magnet behaviours. A simple, almost visual analysis of the chemical shifts as a function of temperature, which is at the core of this approach, allows for a correct signal assignment and evaluation of the anisotropy of the magnetic susceptibility, the key indicator of a good single molecule magnet, that often cannot be done using traditional techniques rooted in quantum chemistry and NMR spectroscopy. The proposed approach thus emerged as a powerful alternative in deciphering the NMR spectra of paramagnetic compounds for applications in data processing and storage, magnetic resonance imaging and structural biology.

14.
Nanomaterials (Basel) ; 11(8)2021 Jul 22.
Artigo em Inglês | MEDLINE | ID: mdl-34443706

RESUMO

A technology for the formation of electrically conductive nanostructures from single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), and their hybrids with reduced graphene oxide (rGO) on Si substrate has been developed. Under the action of single pulses of laser irradiation, nanowelding of SWCNT and MWCNT nanotubes with graphene sheets was obtained. Dependences of electromagnetic wave absorption by films of short and long nanotubes with subnanometer and nanometer diameters on wavelength are calculated. It was determined from dependences that absorption maxima of various types of nanotubes are in the wavelength region of about 266 nm. It was found that contact between nanotube and graphene was formed in time up to 400 fs. Formation of networks of SWCNT/MWCNT and their hybrids with rGO at threshold energy densities of 0.3/0.5 J/cm2 is shown. With an increase in energy density above the threshold value, formation of amorphous carbon nanoinclusions on the surface of nanotubes was demonstrated. For all films, except the MWCNT film, an increase in defectiveness after laser irradiation was obtained, which is associated with appearance of C-C bonds with neighboring nanotubes or graphene sheets. CNTs played the role of bridges connecting graphene sheets. Laser-synthesized hybrid nanostructures demonstrated the highest hardness compared to pure nanotubes. Maximum hardness (52.7 GPa) was obtained for MWCNT/rGO topology. Regularity of an increase in electrical conductivity of nanostructures after laser irradiation has been established for films made of all nanomaterials. Hybrid structures of nanotubes and graphene sheets have the highest electrical conductivity compared to networks of pure nanotubes. Maximum electrical conductivity was obtained for MWCNT/rGO hybrid structure (~22.6 kS/m). Networks of nanotubes and CNT/rGO hybrids can be used to form strong electrically conductive interconnections in nanoelectronics, as well as to create components for flexible electronics and bioelectronics, including intelligent wearable devices (IWDs).

15.
Chem Sci ; 12(10): 3682-3692, 2021 Jan 15.
Artigo em Inglês | MEDLINE | ID: mdl-34163642

RESUMO

The reaction between basic [(PCP)Pd(H)] (PCP = 2,6-(CH2P(t-C4H9)2)2C6H4) and acidic [LWH(CO)3] (L = Cp (1a), Tp (1b); Cp = η5-cyclopentadienyl, Tp = κ3-hydridotris(pyrazolyl)borate) leads to the formation of bimolecular complexes [LW(CO)2(µ-CO)⋯Pd(PCP)] (4a, 4b), which catalyze amine-borane (Me2NHBH3, t BuNH2BH3) dehydrogenation. The combination of variable-temperature (1H, 31P{1H}, 11B NMR and IR) spectroscopies and computational (ωB97XD/def2-TZVP) studies reveal the formation of an η1-borane complex [(PCP)Pd(Me2NHBH3)]+[LW(CO3)]- (5) in the first step, where a BH bond strongly binds palladium and an amine group is hydrogen-bonded to tungsten. The subsequent intracomplex proton transfer is the rate-determining step, followed by an almost barrierless hydride transfer. Bimetallic species 4 are easily regenerated through hydrogen evolution in the reaction between two hydrides.

16.
Dalton Trans ; 50(11): 3786-3791, 2021 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-33704306

RESUMO

Solution behaviour in DMSO using 1D and 2D NMR spectroscopy was performed for lanthanide complexes Ln(L)(HL) and Ln(HL)2Cl, containing non-macrocyclic 2-(tosylamino)-benzylidene-N-benzoylhydrazone (H2L), and the structure of [Yb(L)]+ cation in solution was determined. Based on the NMR data, the possibility to obtain novel complexes containing [Ln(L)2]- was predicted, which was successfully synthesized, and the crystal structure of K(C2H5OH)3[Yb(L)2] was determined. Thanks to its high quantum yield of NIR luminescence (1.3 ± 0.2%), high absorption, low toxicity, and the stability of its anion against dissociation in DMSO, K(H2O)3[Yb(L)2] was successfully used for bioimaging.


Assuntos
Complexos de Coordenação/química , Hidrazonas/química , Imagem Óptica , Itérbio/química , Ânions/química , Linhagem Celular , Complexos de Coordenação/síntese química , Humanos , Raios Infravermelhos , Estrutura Molecular , Soluções
17.
Sci Rep ; 11(1): 4790, 2021 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-33637821

RESUMO

Unique and flexible properties of non-Hermitian photonic systems attract ever-increasing attention via delivering a whole bunch of novel optical effects and allowing for efficient tuning light-matter interactions on nano- and microscales. Together with an increasing demand for the fast and spatially compact methods of light governing, this peculiar approach paves a broad avenue to novel optical applications. Here, unifying the approaches of disordered metamaterials and non-Hermitian photonics, we propose a conceptually new and simple architecture driven by disordered loss-gain multilayers and, therefore, providing a powerful tool to control both the passage time and the wave-front shape of incident light with different switching times. For the first time we show the possibility to switch on and off kink formation by changing the level of disorder in the case of adiabatically raising wave fronts. At the same time, we deliver flexible tuning of the output intensity by using the nonlinear effect of loss and gain saturation. Since the disorder strength in our system can be conveniently controlled with the power of the external pump, our approach can be considered as a basis for different active photonic devices.

18.
Dalton Trans ; 50(1): 287-293, 2021 Jan 07.
Artigo em Inglês | MEDLINE | ID: mdl-33300519

RESUMO

Thirteen new metallacarborane complexes of rhodium and iridium with covalently bound cage carbon atoms were synthesized and their thermal stability was investigated. Two iridium complexes undergo a polyhedral rearrangement with the formation of more than one isomer. The structures of the new isomers were determined by a single crystal X-ray diffraction analysis and 11B{1H}-11B{1H} COSY NMR. A full isomerization scheme of the less thermally stable complex was proposed based on DFT calculations. According to this mechanism sequential downhill and uphill bifurcations arise in the reaction pathway. Each bifurcation is responsible for a new product formation.

19.
Inorg Chem ; 59(17): 11962-11975, 2020 Sep 08.
Artigo em Inglês | MEDLINE | ID: mdl-32806008

RESUMO

Two stereoisomers of pentacoordinate iridium(III) hydridochloride with triptycene-based PC(sp3)P pincer ligand (1,8-bis(diisopropylphosphino)triptycene), 1 and 2, differ by the orientation of hydride ligand relative to the bridgehead ring of triptycene. According to DFT/B3PW91/def2-TZVP calculations performed, an equatorial Cl ligand can relatively easily change its position in 1, whereas that is not the case in 2. Both complexes 1 and 2 readily bind the sixth ligand to protect the empty coordination site. Variable temperature spectroscopic (NMR, IR, and UV-visible) studies show the existence of two isomers of hexacoordinate complexes 1·MeCN, 2·MeCN, and 2·Py with acetonitrile or pyridine coordinated trans to hydride or trans to metalated C(sp3), whereas only the equatorial isomer is found for 1·Py. These complexes are stabilized by various intramolecular noncovalent C-H···Cl interactions that are affected by the rotation of isopropyls or pyridine. The substitution of MeCN by pyridine is slow yielding axial Py complexes as kinetic products and the equatorial Py complexes as thermodynamic products with faster reactions of 1·L. Ultimately, that explains the higher activity of 1 in the catalytic alkenes' isomerization observed for allylbenzene, 1-octene, and pent-4-enenitrile, which proceeds as an insertion/elimination sequence rather than through the allylic mechanism.

20.
Int J Mol Sci ; 21(17)2020 Aug 26.
Artigo em Inglês | MEDLINE | ID: mdl-32859107

RESUMO

The coating formation technique for artificial knee ligaments was proposed, which provided tight fixation of ligaments of polyethylene terephthalate (PET) fibers as a result of the healing of the bone channel in the short-term period after implantation. The coating is a frame structure of single-walled carbon nanotubes (SWCNT) in a collagen matrix, which is formed by layer-by-layer solidification of an aqueous dispersion of SWCNT with collagen during spin coating and controlled irradiation with IR radiation. Quantum mechanical method SCC DFTB, with a self-consistent charge, was used. It is based on the density functional theory and the tight-binding approximation. The method established the optimal temperature and time for the formation of the equilibrium configurations of the SWCNT/collagen type II complexes to ensure maximum binding energies between the nanotube and the collagen. The highest binding energies were observed in complexes with SWCNT nanometer diameter in comparison with subnanometer SWCNT. The coating had a porous structure-pore size was 0.5-6 µm. The process of reducing the mass and volume of the coating with the initial biodegradation of collagen after contact with blood plasma was demonstrated. This is proved by exceeding the intensity of the SWCNT peaks G and D after contact with the blood serum in the Raman spectrum and by decreasing the intensity of the main collagen bands in the SWCNT/collagen complex frame coating. The number of pores and their size increased to 20 µm. The modification of the PET tape with the SWCNT/collagen coating allowed to increase its hydrophilicity by 1.7 times compared to the original PET fibers and by 1.3 times compared to the collagen coating. A reduced hemolysis level of the PET tape coated with SWCNT/collagen was achieved. The SWCNT/collagen coating provided 2.2 times less hemolysis than an uncoated PET implant. MicroCT showed the effective formation of new bone and dense connective tissue around the implant. A decrease in channel diameter from 2.5 to 1.7 mm was detected at three and, especially, six months after implantation of a PET tape with SWCNT/collagen coating. MicroCT allowed us to identify areas for histological sections, which demonstrated the favorable interaction of the PET tape with the surrounding tissues. In the case of using the PET tape coated with SWCNT/collagen, more active growth of connective tissue with mature collagen fibers in the area of implantation was observed than in the case of only collagen coating. The stimulating effect of SWCNT/collagen on the formation of bone trabeculae around and inside the PET tape was evident in three and six months after implantation. Thus, a PET tape with SWCNT/collagen coating has osteoconductivity as well as a high level of hydrophilicity and hemocompatibility.


Assuntos
Osso Esponjoso/efeitos dos fármacos , Colágeno/farmacologia , Ligamentos/transplante , Polietilenotereftalatos/química , Animais , Bioprótese , Regeneração Óssea/efeitos dos fármacos , Osso Esponjoso/cirurgia , Colágeno/química , Nanotubos de Carbono/química , Tamanho da Partícula , Teoria Quântica , Coelhos , Cicatrização/efeitos dos fármacos
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA