Theoretical study of cobalt and nickel complexes involved in methyl transfer reactions: structures,redox potentials and methyl binding energies

Structural Chemistry - Cobalamins, cobalt glyoximate complexes and nickel complexes with Triphos (bis(diphenylphosphinoethyl)phenylphosphine) and PPh2CH2CH2SEt ligands were studied with the...     

A least-squares method for second order noncoercive elliptic partial differential equations

In this paper, we consider a least-squares method proposed by Bramble, Lazarov and Pasciak (1998) which can be thought of as a stabilized Galerkin method for noncoercive problems with unique solutions. We modify their method by weakening the strength of the stabilization terms and present various new error estimates. The modified method has all the desirable properties of the original method; indeed, we shall show some theoretical properties that are not known for the original method. At the same time, our numerical experiments show an improvement of the method due to the modification.

     

Functionalization of vinyl-substituted linear oligo- and polysiloxanes via ruthenium catalyzed silylative coupling with styrene

Efficient silylative coupling of linear vinyl-substituted oligo- and polysiloxanes with styrene in the presence of [RuHCl(CO)(PPh₃)₃] (1) and particularly [RuHCl(CO)(PCy₃)₂] (2) combined with copper(I) chloride is described. Treatment of styrene, with terminal or side vinyl group at siloxane skeleton catalyzed by [RuHCl(CO)(PCy₃)₂]/CuCl results in the quantitative and selective formation of respective silylative coupling products.     

Short-length and broadband mismatched optical couplers with tapered Hamming function for C- and L-band

Mismatched optical couplers with variable widths of waveguide tapered by Hamming function are numerically investigated in the demand of short-length, broadband, and low crosstalk. We used global search algorithm and beam propagation method to seek optimal structure parameters of coupling waveguide. The coupler length is 3.6 mm within the C+L-band (1.53-1.61 μm) for variable widths of waveguide at crosstalk level of −35 dB. Comparison with constant width of waveguide, the constant width of waveguide has a coupler length of 4.4 mm and can only achieve −20 dB of crosstalk within the C-band (1.53-1.565 μm). Obviously, the waveguide with variable widths has the advantage over constant width for the demand of short-length, bandwidth, and low-crosstalk.     

Physicochemical Properties and Surface Characteristics of Ground Human Teeth

Enamel, dentin and cementum apatite has a complex composition. The lack of complete reports on the chemical composition of all tooth tissues together and the need to create a modern biomaterial that reproduces the correct ratio of individual tooth mineral components prompted the authors to undertake the research. A detailed evaluation of the micro- and macro-elements of tooth powder, using various methods of chemical analysis was conducted. All four groups of human sound teeth were crushed using the grinder. A fine powder was implemented for the FTIR (Fourier Transform Infrared Spectroscopy), ICP (Inductively Coupled Plasma Optical Emission Spectometry) and for the potentiometric titration, SEM and mercury porosimetry analyses. The obtained studies indicate that there is no significant correlation in chemical composition between the different teeth types. This proves that every removed, crushed tooth free of microorganisms can be a suitable material for alveolar augmentation. It is essential to know the chemical profiles of different elements in teeth to develop a new class of biomaterials for clinical applications.     

Effect of Heavy Metal Stress on Phenolic Compounds Accumulation in Winter Wheat Plants

Heavy metal stress can lead to many adverse effects that inhibit cellular processes at various levels of metabolism, causing a decrease in plant productivity. In response to environmental stressors, phenolic compounds fulfill significant molecular and biochemical functions in plants. Increasing the biosynthesis of phenolic compounds in plants subjected to heavy metal stress helps protect plants from oxidative stress. A pot experiment was carried out to determine the effect of the accumulation of copper (Cu) and lead (Pb) salts at concentrations of 200, 500, and 1000 ppm on seed germination, the activity of enzymes in the phenylalanine ammonia-lyase pathway (PAL) and tyrosine ammonia-lyase (TAL), along with the total phenol and flavonoid contents in seedlings of hybrid Triticum aestivum L. (winter wheat) cultivars. The accumulation of heavy metals, especially Cu, had a negative impact on the seed germination process. The cultivar “Hyacinth” reacted most strongly to heavy metal stress, which was confirmed by obtaining the lowest values of the germination parameters. Heavy metal stress caused an increase in the activity of PAL and TAL enzymes and an increase in the accumulation of phenolic compounds. Under the influence of Cu, the highest activity was shown in cv. “Hyvento” (especially at 200 ppm) and, due to the accumulation of Pb, in cv. “Hyacinth” (1000 ppm) and cv. “Hyking” (200 ppm). The cultivar “Hyking” had the highest content of phenolic compounds, which did not increase with the application of higher concentrations of metals. In other cultivars, the highest content of total phenols and flavonoids was usually observed at the lowest concentration (200 ppm) of the tested heavy metals, Cu and Pb.     

Diketopiperazine-Based,Flexible Tadalafil Analogues: Synthesis,Crystal Structures and Biological Activity Profile

Phosphodiesterase 5 (PDE5) is one of the most extensively studied phosphodiesterases that is highly specific for cyclic-GMP hydrolysis. PDE5 became a target for drug development based on its efficacy for treatment of erectile dysfunction. In the present study, we synthesized four novel analogues of the phosphodiesterase type 5 (PDE5) inhibitor—tadalafil, which differs in (i) ligand flexibility (rigid structure of tadalafil vs. conformational flexibility of newly synthesized compounds), (ii) stereochemistry associated with applied amino acid building blocks, and (iii) substitution with bromine atom in the piperonyl moiety. For both the intermediate and final compounds as well as for the parent molecule, we have established the crystal structures and performed a detailed analysis of their structural features. The initial screening of the cytotoxic effect on 16 different human cancer and non-cancer derived cell lines revealed that in most cases, the parent compound exhibited a stronger cytotoxic effect than new derivatives, except for two cell lines: HEK 293T (derived from a normal embryonic kidney, that expresses a mutant version of SV40 large T antigen) and MCF7 (breast adenocarcinoma). Two independent studies on the inhibition of PDE5 activity, based on both pure enzyme assay and modulation of the release of nitric oxide from platelets under the influence of tadalafil and its analogues revealed that, unlike a reference compound that showed strong PDE5 inhibitory activity, the newly obtained compounds did not have a noticeable effect on PDE5 activity in the range of concentrations tested. Finally, we performed an investigation of the toxicological effect of synthesized compounds on Caenorhabditis elegans in the highest applied concentration of 6a,b and 7a,b (160 μM) and did not find any effect that would suggest disturbance to the life cycle of Caenorhabditis elegans. The lack of toxicity observed in Caenorhabditis elegans and enhanced, strengthened selectivity and activity toward the MCF7 cell line made 7a,b good leading structures for further structure activity optimization and makes 7a,b a reasonable starting point for the search of new, selective cytotoxic agents.     

N-Phenacyldibromobenzimidazoles—Synthesis Optimization and Evaluation of Their Cytotoxic Activity

Antifungal N-phenacyl derivatives of 4,6- and 5,6-dibromobenzimidazoles are interesting substrates in the synthesis of new antimycotics. Unfortunately, their application is limited by the low synthesis yields and time-consuming separation procedure. In this paper, we present the optimization of the synthesis conditions and purification methods of N-phenacyldibromobenzimidazoles. The reactions were carried out in various base solvent-systems including K₂CO₃, NaH, KOH, t-BuOK, MeONa, NaHCO₃, Et₃N, Cs₂CO₃, DBU, DIPEA, or DABCO as a base, and MeCN, DMF, THF, DMSO, or dioxane as a solvent. The progress of the reaction was monitored using HPLC analysis. The best results were reached when the reactions were carried out in an NaHCO₃–MeCN system at reflux for 24 h. Additionally, the cytotoxic activity of the synthesized compounds against MCF-7 (breast adenocarcinoma), A-549 (lung adenocarcinoma), CCRF-CEM (acute lymphoblastic leukemia), and MRC-5 (normal lung fibroblasts) was evaluated. We observed that the studied cell lines differed in sensitivity to the tested compounds with MCF-7 cells being the most sensitive, while A-549 cells were the least sensitive. Moreover, the cytotoxicity of the tested derivatives towards CCRF-CEM cells increased with the number of chlorine or fluorine substituents. Furthermore, some of the active compounds, i.e., 2-(5,6-dibromo-1H-benzimidazol-1-yl)-1-(3,4-dichlorophenyl)ethanone (4f), 2-(4,6-dibromo-1H-benzimidazol-1-yl)-1-(2,4,6-trichlorophenyl)ethanone (5g), and 2-(4,6-dibromo-1H-benzimidazol-1-yl)-1-(2,4,6-trifluorophenyl)ethanone (5j) demonstrated pro-apoptotic properties against leukemic cells with derivative 5g being the most effective.     

Zirconia—A stationary phase capable of the separation of polar markers of myocardial metabolism in hydrophilic interaction chromatography

Creatine, phosphocreatine, and adenine nucleotides are highly polar markers of myocardial metabolism that are poorly retained on RP silica sorbents. Zirconia represents an alternative material to silica with high promise to be used in hydrophilic interaction chromatography (HILIC). This study describes a first systematic investigation of the ability of ZrO₂ to separate creatine, phosphocreatine, adenosine 5′‐monophosphate, adenosine 5′‐diphosphate, and adenosine 5′‐triphosphate and compares the results with those obtained on TiO₂. All analytes showed a HILIC‐like retention pattern when mobile phases of different strengths were tested. Stronger retention and better column performance were achieved in organic‐rich mobile phases as compared to aqueous conditions, where poor retention and insufficient column performance were observed. The effect of mobile phase pH and ionic strength was evaluated as well. The analysis of myocardial tissue demonstrated that all compounds were separated in a relevant biological material and thus proved ZrO₂ as a promising phase for HILIC of biological samples that deserves further investigation.     

Nickel determination in biological materials at ultratrace level by fast neutron radiochemical activation analysis

Using radiochemical separation of cobalt following the fast neutron reaction⁵⁸Ni(n, p.)⁵⁸Co and long high fluence irradiation, we attempted to improve the determination limit for Ni to the nanogram and sub-nanogram level. A Compton suppression spectrometer was shown to be the best choice compared to co-axial or well-type HPGe detectors. Results for low level biological reference materials such as serum and milk powder are discussed. Use of both dried and pre-ashed samples showed that losses of Ni and Co on ashing are non-significant. The influence of the silica ampoule blank was also investigated.