RESUMO
Sodium pectate derivatives with 25% replacement of sodium ions with nickel ions were obtained by carbonization to temperatures of 280, 550, and 800 °C, under special protocols in an inert atmosphere by carbonization to temperatures of 280, 550, and 800 °C. The 25% substitution is the upper limit of substitution of sodium for nickel ions, above which the complexes are no longer soluble in water. It was established that the sample carburized to 550 °C is the most effective active element in the hydrogen-oxidation reaction, while the sample carbonized up to 800 °C was the most effective in the oxygen-reduction reaction. The poor performance of the catalytic system involving the pectin coordination biopolymer carbonized up to 280 °C was due to loss of proton conductivity caused by water removal and mainly by two-electron transfer in one catalytic cycle of the oxygen-reduction reaction. The improved performance of the system with coordination biopolymer carbonized up to 550 °C was due to the better access of gases to the catalytic sites and four-electron transfer in one catalytic cycle. The (Ni-NaPG)800C sample contains metallic nickel nanoparticles and loose carbon, which enhances the electrical conductivity and gas capacity of the catalytic system. In addition, almost four-electron transfer is observed in one catalytic cycle of the oxygen-reduction reaction.
RESUMO
This work aimed to obtain an optically transparent electrode based on the oriented nanonetworks of nickel in poly(3,4-ethylenedioxythiophene) polystyrene sulfonate matrix. Optically transparent electrodes are used in many modern devices. Therefore, the search for new inexpensive and environmentally friendly materials for them remains an urgent task. We have previously developed a material for optically transparent electrodes based on oriented platinum nanonetworks. This technique was upgraded to obtain a cheaper option from oriented nickel networks. The study was carried out to find the optimal electrical conductivity and optical transparency values of the developed coating, and the dependence of these values on the amount of nickel used was investigated. The figure of merit (FoM) was used as a criterion for the quality of the material in terms of finding the optimal characteristics. It was shown that doping PEDOT: PSS with p-toluenesulfonic acid in the design of an optically transparent electroconductive composite coating based on oriented nickel networks in a polymer matrix is expedient. It was found that the addition of p-toluenesulfonic acid to an aqueous dispersion of PEDOT: PSS with a concentration of 0.5% led to an eight-fold decrease in the surface resistance of the resulting coating.
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Brain tumor glioblastoma is one of the worst types of cancer. The blood-brain barrier prevents drugs from reaching brain cells and shields glioblastoma from treatment. The creation of nanocarriers to improve drug delivery and internalization effectiveness may be the solution to this issue. In this paper, we report on a new nanocarrier that was developed to deliver the anticancer drug doxorubicin to glioblastoma cells. The nanocarrier was obtained by nanoemulsion polymerization of diallyl disulfide with 1-allylthymine. Diallyl disulfide is a redox-sensitive molecule involved in redox cell activities, and thymine is a uracil derivative and one of the well-known bioactive compounds that can enhance the pharmacological activity of doxorubicin. Doxorubicin was successfully introduced into the nanocarrier with a load capacity of about 4.6%. Biological studies showed that the doxorubicin nanocarrier composition is far more cytotoxic to glioblastoma cells (T98G) than it is to cancer cells (M-HeLa) and healthy cells (Chang liver). The nanocarrier improves the penetration of doxorubicin into T98G cells and accelerates the cells' demise, as is evident from flow cytometry and fluorescence microscopy data. The obtained nanocarrier, in our opinion, is a promising candidate for further research in glioblastoma therapy.
Assuntos
Antineoplásicos , Neoplasias Encefálicas , Glioblastoma , Nanopartículas , Humanos , Timina , Portadores de Fármacos/uso terapêutico , Glioblastoma/tratamento farmacológico , Doxorrubicina , Sistemas de Liberação de Medicamentos , Antineoplásicos/uso terapêutico , Neoplasias Encefálicas/tratamento farmacológicoRESUMO
A number of nickel complexes of sodium pectate with varied Ni2+ content have been synthesized and characterized. The presence of the proton conductivity, the possibility of the formation of a dense spatial network of transition metals in these coordination biopolymers, and the immobilization of transition ions in the catalytic sites of this class of compounds make them promising for proton-exchange membrane fuel cells. It has been established that the catalytic system composed of a coordination biopolymer with 20% substitution of sodium ions for divalent nickel ions, Ni (20%)-NaPG, is the leading catalyst in the series of 5, 15, 20, 25, 35% substituted pectates. Among the possible reasons for the improvement in performance the larger specific surface area of this sample compared to the other studied materials and the narrowest distribution of the vertical size of metal arrays were registered. The highest activity during CV and proximity to four-electron transfer during the catalytic cycle have also been observed for this compound.
Assuntos
Níquel , Prótons , Pectinas , OxigênioRESUMO
The present work introduces rational design of nanoparticulate Mn(II)-based contrast agents through both variation of the µ3 (inner) ligands within a series of hexarhenium cluster complexes [{Re6(µ3-Q)8}(CN)6]4- (Re6Q8, Q = S2-, Se2- or Te2-) and interfacial decoration of the nanoparticles (NPs) K4-2xMnxRe6Q8 (x = 1.3 - 1.8) by a series of pluronics (F-68, P-123, F-127). The results highlight an impact of the ligand and pluronic for the optimal colloid behavior of the NPs allowing high colloid stability in ambient conditions and efficient phase separation under the centrifugation. It has been revealed that the K4-2xMnxRe6Se8 NPs and those decorated by F-127 are optimal from the viewpoint of magnetic relaxivities r1 and r2 (8.9 and 10.9 mM-1s-1, respectively, at 0.47 T) and low hemoagglutination activity. The insignificant leaching of Mn2+ ions from the NPs correlates with their insignificant effect on the cell viability of both M-HeLa and Chang Liver cell lines. The T1- and T2-weighted contrast ability of F-127-K4-2xMnxRe6Q8 NPs was demonstrated through the measurements of phantoms at whole body 1.5 T scanner.
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Novel cationic amphiphiles of the 3-alkyl-1-(4-methoxyphenyl)-1H-imidazol-3-ium bromide series bearing methoxyphenyl fragments (MPI-n) have been synthesized. Their aggregation properties in aqueous solutions, solubilization capacity, and hemolytic and antimicrobial activities have been investigated by a number of physicochemical methods. Using tensiometry, conductometry, and fluorescence spectroscopy, it was shown that the MPI-n have lower CMCs than their nonfunctionalized counterparts. The unusual alkyl-chain-length-dependent morphology of aggregates is testified for this homological series. Amphiphiles with 12, 14, and 16 alkyl tails are characterized by the formation of micellar aggregates, while a surfactant with a decyl tail is characterized by the formation of larger aggregates with lower surface curvature. The MPI-10 aggregate morphology was rationalized in terms of the packing parameter consideration and was supported by size measurements and the fluorescence probe techniques, which showed that vesicle-like aggregates in close-packing mode probably occur. MPI-n aggregates have exhibited a high solubilization capacity toward hydrophobic azo dye Orange OT. Importantly, amphiphiles studied showed (i) high bacteriostatic activity at the level of ciprofloxacin; (ii) high bactericidal action against all Gram-positive bacteria, including methicillin-resistant strains; (iii) bactericidal properties against Gram-negative bacteria; and (iv) low hemolytic activity.
Assuntos
Micelas , Tensoativos , Antibacterianos/farmacologia , Cátions , Interações Hidrofóbicas e Hidrofílicas , Tensoativos/química , Tensoativos/farmacologiaRESUMO
New 1-cetyl-4-aza-1-azoniabicyclo[2.2.2]octane bromide complexes with copper(II) bromide and lanthanum(III) nitrate were characterized using dynamic light scattering and transmission electron microscopy, with self-assembly and the morphological behavior elucidated. For the lanthanum(III) nitrate complex, the 3D crystal structure was characterized using X-ray diffractometry. These metallosurfactants were tested as antitumor agents, and a high cytotoxic effect comparable with doxorubicin was revealed against the M-HeLa and A-549 cell lines. Both complexes were 2 times more active toward the MCF-7 cell line than the breast cancer drug tamoxifen. The cytotoxic mechanism of complexes is assumed to be related to the induction of apoptosis through the mitochondrial pathway.
RESUMO
A selective noble-metal-free molecular catalyst has emerged as a fruitful approach in the quest for designing efficient and stable catalytic materials for CO2 reduction. In this work, we report that a sodium pectate complex of copper (PG-NaCu) proved to be highly active in the electrocatalytic conversion of CO2 to CH4 in water. Stability and selectivity of conversion of CO2 to CH4 as a product at a glassy carbon electrode were discovered. The copper complex PG-NaCu was synthesized and characterized by physicochemical methods. The electrochemical CO2 reduction reaction (CO2RR) proceeds at -1.5 V vs. Ag/AgCl at ~10 mA/cm2 current densities in the presence of the catalyst. The current density decreases by less than 20% within 12 h of electrolysis (the main decrease occurs in the first 3 h of electrolysis in the presence of CO2). This copper pectate complex (PG-NaCu) combines the advantages of heterogeneous and homogeneous catalysts, the stability of heterogeneous solid materials and the performance (high activity and selectivity) of molecular catalysts.
RESUMO
New liposomes modified with pyrrolidinium surfactants containing a hydroxyethyl fragment (CnPB, n = 12, 14, 16) were prepared for transdermal delivery of non-steroidal anti-inflammatory drugs. In order to obtain the optimal composition, the surfactant/lipid molar ratio (0.02/1; 0.029/1; 0.04/1) and the amphiphile hydrocarbon tail length were varied. Rhodamine B was loaded in all formulations, while meloxicam and ketoprofen in selected ones. For liposomes studied the hydrodynamic diameter was in the range of 80-130 nm, the zeta potential ranged from +35 to +50 mV, EE was 75-99%. Liposome modification leads to a prolonged release of the rhodamine B (up to 10-12 h) and faster release of non-steroidal drugs (up to 7-8 h) in vitro. The ability to cross the skin barrier using Franz cells was investigated for liposomal meloxicam and ketoprofen. The total amount of meloxicam and ketoprofen passed through the Strat-M® membranes during 51 h was 51-114 µg/cm2 and 87-105 µg/cm2 respectively. The evaluation of transdermal diffusion ex vivo showed that total amount of liposomal ketoprofen passed through the skin during 51 h was 140-162 µg/cm2. Liposomes modified with C16PB were found as the most effective inflammation reducing formulation in the carrageenan edema model of rat paw.
Assuntos
Cetoprofeno , Lipossomos , Administração Cutânea , Animais , Anti-Inflamatórios não Esteroides , Meloxicam , Tamanho da Partícula , Ratos , PeleRESUMO
The paper demonstrates a technique for applying an oriented nickel network to a glass surface. The method is based on the chemical reduction of nickel salt. The shaping and orientation of the resulting system are carried out using a micellar template of a surfactant and a magnetic field. Submicron nickel fibres are used to impart unity to the plurality of individual-oriented nickel nanonetworks. The result is a single conductive coating on the surface of the glass, which has a transparency in the optical range. Investigations of the structure, chemical composition, morphology and electrical conductivity of the coating were performed.
RESUMO
The addition of specific chemical groups in a macrocycle structure influences its functional properties and, consequently, can provide new possibilities, among which are aggregation properties, water solubility, biocompatibility, stimuli response, biological activity, etc. Herein, we report synthesis of new resorcin[4]arene with N-methyl-d-glucamine groups on the upper rim and n-decyl chains on the lower rim, an investigation of its self-assembly behavior in aqueous media, and its use as a building block for the formation of drug nanocontainer. N-methyl-d-glucamine fragments in the resorcin[4]arene structure promote higher stability in solutions, simplification of self-aggregation, and increased biological activity. Antimicrobial and hemolytic activity assessment revealed that this resorcin[4]arene obtained is nontoxic. The study of cell penetration was carried out with both free and encapsulated doxorubicin (DOX). Surprisingly, DOX-loaded macrocycle aggregates are more efficient in causing apoptosis in human cancer cell line. Conceivably, this knowledge will help in the rational design of DOX combination for novel drug-administration strategies in cancer treatment.
Assuntos
Apoptose/efeitos dos fármacos , Calixarenos/química , Portadores de Fármacos/química , Nanopartículas/química , Antibióticos Antineoplásicos/administração & dosagem , Calixarenos/síntese química , Linhagem Celular Tumoral , Doxorrubicina/administração & dosagem , Hepatócitos/efeitos dos fármacos , Humanos , Microscopia Eletrônica de Transmissão , Nanopartículas/ultraestrutura , SolubilidadeRESUMO
Deep insight of the toxicity of supramolecular systems based on macrocycles is of fundamental interest because of their importance in biomedical applications. What seems to be most interesting in this perspective is the development of the macrocyclic compounds with biocompatible fragments. Here, calix[4]resorcinarene derivatives containing N-methyl- d-glucamine moieties at the upper rim and different chemical groups at the lower rim were synthesized and investigated. These macrocycles showed a tendency to self-aggregate in aqueous solution, and their self-assembly abilities depend on the structure of the lower rim. The in vitro cytotoxic and antimicrobial activity of the calix[4]resorcinarenes revealed the relationship of biological properties with the ability to aggregate. Compared to macrocycles with methyl groups on the lower rim, calix[4]resorcinarenes with sulfonate groups appear to possess very similar antibacterial properties, but over six times less hemolytic activity. In some ways, this is the first example that reveals the dependence of the observed hemolytic and antibacterial activity on the lipophilicity of the calix[4]arene structure.
Assuntos
Calixarenos/química , Calixarenos/farmacologia , Fenilalanina/análogos & derivados , Antibacterianos/farmacologia , Calixarenos/síntese química , Morte Celular/efeitos dos fármacos , Difusão , Condutividade Elétrica , Humanos , Compostos Macrocíclicos/química , Tamanho da Partícula , Fenilalanina/síntese química , Fenilalanina/química , Fenilalanina/farmacologia , Eletricidade Estática , Tensão SuperficialRESUMO
Novel liposomes based on 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and imidazolium-containing amphiphiles with various length of hydrophobic tail at various molar ratio of components have been fabricated. Obtained formulations were characterized using dynamic and electrophoretic light scattering as well as transmission electron microscopy techniques. It has been established, that DPPC liposomes modification by these cationic amphiphiles resulted in zeta potential increase from +3 mV to +45-70 mV and improve its stability for a long time (more than 6 months, whereas unmodified liposomes have been destructed after 2 weeks of storage). Hydrodynamic diameter of prepared hybrid liposomes was in the range of 70-100 nm depending on its composition. Fabricated hybrid carriers have been used for drug (metronidazole) encapsulation. It has been shown, that superior encapsulation characteristics (encapsulation efficiency was 75%) exhibited hybrid liposomes composed from octadecyl derivative. Increase of the time of total release of encapsulated drug from hybrid liposomes in comparison with unencapsulated drug by 1.7 times has been demonstrated.
Assuntos
1,2-Dipalmitoilfosfatidilcolina/química , Portadores de Fármacos/química , Lipossomos/química , Imidazóis/química , Metronidazol/químicaRESUMO
A nanocarrier (p(6SRA-5B)) for glucose-controlled insulin delivery consists of sulfonated resorcinarenes (SRA) that are assembled into a spherical shell and are attached to each other with phenylboronate linkers. p(6SRA-5B) is stable in water and blood plasma at normal glucose concentrations. At high glucose levels (>5â mM), p(6SRA-5B) dissociates into SRA and phenylboronates through competitive interaction with excess glucose. Insulin was successfully encapsulated into the cavity of p(6SRA-5B) and its release was investigated in water and blood plasma by NMR, UV, CD, and fluorescence spectroscopy. The results show that the dissociation of the nanocarrier and the insulin release occurs with an increase in glucose concentration. At 5â mM glucose, the nanocarrier is stable, and the insulin release does not exceed 10 %. Increasing the glucose concentration to 7.5-10â mM results in a 40-100 % insulin release. p(6SRA-5B) is thus a promising insulin nanocarrier for the treatment of type 1 diabetes.
Assuntos
Calixarenos/química , Portadores de Fármacos/química , Sistemas de Liberação de Medicamentos/métodos , Glucose/farmacologia , Insulina/administração & dosagem , Fenilalanina/análogos & derivados , Ácidos Borônicos/química , Diabetes Mellitus Tipo 1/tratamento farmacológico , Liberação Controlada de Fármacos/efeitos dos fármacos , Humanos , Fenilalanina/química , Polímeros/química , Ácidos Sulfônicos/químicaRESUMO
New mixed cationic liposomes based on L-α-phosphatidylcholine and dihexadecylmethylhydroxyethylammonium bromide (DHDHAB) were designed to overcome the BBB crossing by using the intranasal route. Synthesis and self-assembly of DHDHAB were performed. A low critical association concentration (0.01 mM), good solubilization properties toward hydrophobic dye Orange OT and antimicrobial activity against gram-positive bacteria Staphylococcus aureus (MIC=7.8 µg mL-1) and Bacillus cereus (MIC=7.8 µg mL-1), low hemolytic activities against human red blood cells (less than 10%) were achieved. Conditions for preparation of cationic vesicles and mixed liposomes with excellent colloidal stability at room temperature were determined. The intranasal administration of rhodamine B-loaded cationic liposomes was shown to increase bioavailability into the brain in comparison to the intravenous injection. The cholinesterase reactivator, 2-PAM, was used as model drug for the loading in cationic liposomes. 2-PAM-loaded cationic liposomes displayed high encapsulation efficiency (â¼ 90%) and hydrodynamic diameter close to 100 nm. Intranasally administered 2-PAM-loaded cationic liposomes were effective against paraoxon-induced acetylcholinesterase inhibition in the brain. 2-PAM-loaded liposomes reactivated 12 ± 1% of brain acetylcholinesterase. This promising result opens the possibility to use marketed positively charged oximes in medical countermeasures against organophosphorus poisoning for reactivation of central acetylcholinesterase by implementing a non-invasive approach, via the "nose-brain" pathway.
Assuntos
Antibacterianos/farmacologia , Encéfalo/efeitos dos fármacos , Reativadores da Colinesterase/farmacologia , Sistemas de Liberação de Medicamentos , Compostos de Pralidoxima/farmacologia , Compostos de Amônio Quaternário/farmacologia , Acetilcolinesterase/metabolismo , Administração Intranasal , Antibacterianos/administração & dosagem , Antibacterianos/síntese química , Antibacterianos/química , Bacillus cereus/efeitos dos fármacos , Encéfalo/metabolismo , Cátions/química , Reativadores da Colinesterase/administração & dosagem , Reativadores da Colinesterase/química , Lipossomos/química , Paraoxon/antagonistas & inibidores , Paraoxon/farmacologia , Tamanho da Partícula , Compostos de Pralidoxima/administração & dosagem , Compostos de Pralidoxima/química , Compostos de Amônio Quaternário/síntese química , Compostos de Amônio Quaternário/química , Rodaminas/administração & dosagem , Rodaminas/química , Staphylococcus aureus/efeitos dos fármacos , Propriedades de SuperfícieRESUMO
Novel polymer nanospheres (p(SRA-B)) were prepared by cross-linking a sulfonated resorcinarene (SRA) with phenylboronic acid. p(SRA-B) shows good stability in water and can be used as a nanocontainer for the pH- and glucose-controlled substrate release. Fluorescent dyes (fluorescein, pyrene and 1,3,6,8-pyrenetetrasulfonic acid tetrasodium salt) were successfully loaded into p(SRA-B). The release of dye is achieved by lowering the pH value to 3 or by adding glucose.
RESUMO
Over the last decade isoindigo derivatives have attracted much attention due to their high potential in pharmacy and in the chemistry of materials. In addition, isoindigo derivatives can be modified to form supramolecular structures with tunable morphologies for the use in drug delivery. Amphiphilic long-chain dialkylated isoindigos have the ability to form stable solid nanoparticles via a simple nanoprecipitation technique. Their self-assembly was investigated using tensiometry, dynamic light scattering, spectrophotometry, and fluorometry. The critical association concentrations and aggregate sizes were measured. The hydrophilic-lipophilic balance of alkylated isoindigo derivatives strongly influences aggregate morphology. In the case of short-chain dialkylated isoindigo derivatives, supramolecular polymers of 200 to 700 nm were formed. For long-chain dialkylated isoindigo derivatives, micellar aggregates of 100 to 200 nm were observed. Using micellar surfactant water-soluble forms of monosubstituted 1-hexadecylisoindigo as well as 1,1'-dimethylisoindigo were prepared for the first time. The formation of mixed micellar structures of different types in micellar anionic surfactant solutions (sodium dodecyl sulfate) was determined. These findings are of practical importance and are of potential interest for the design of drug delivery systems and new nanomaterials.
RESUMO
The present work introduces deliberate synthesis of Gd(III)-doped silica nanoparticles with high relaxivity at magnetic field strengths below 1.5T. Modified microemulsion water-in-oil procedure was used in order to achieve superficial localization of Gd(III) complexes within 40-55nm sized silica spheres. The relaxivities of the prepared nanoparticles were measured at 0.47, 1.41 and 1.5T with the use of both NMR analyzer and whole body NMR scanner. Longitudinal relaxivities of the obtained silica nanoparticles reveal significant dependence on the confinement mode, changing from 4.1 to 49.6mM-1s-1 at 0.47T when the localization of Gd(III) complexes changes from core to superficial zones of the silica spheres. The results highlight predominant contribution of the complexes located close to silica/water interface to the relaxivity of the nanoparticles. Low effect of blood proteins on the relaxivity in the aqueous colloids of the nanoparticles was exemplified by serum bovine albumin. T1- weighted MRI data indicate that the nanoparticles provide strong positive contrast at 1.5T, which along with low cytotoxicity effect make a good basis for their application as contrast agents.
Assuntos
Calixarenos/química , Meios de Contraste/síntese química , Gadolínio/química , Imageamento por Ressonância Magnética/métodos , Dióxido de Silício/química , Animais , Bovinos , Sobrevivência Celular/efeitos dos fármacos , Meios de Contraste/farmacologia , Gadolínio/farmacologia , Humanos , Linfócitos/citologia , Linfócitos/efeitos dos fármacos , Espectroscopia de Ressonância Magnética , Nanopartículas/química , Cultura Primária de Células , Soroalbumina Bovina/química , Silanos/químicaRESUMO
Gemini surfactants with hexadecyl tails and hydroxyethylated head groups bridged with tetramethylene (G4), hexamethylene (G6) and dodecamethylene (G12) spacers were shown to self-assemble at the lower critical micelle concentration compared to their conventional m-s-m analogs. The lipoplex formation and the plasmid DNA transfer into different kinds of host cells were studied. In the case of eukaryotic cells, high transfection efficacy has been demonstrated for DNA-gemini complexes, which increased as follows: G6Assuntos
Técnicas de Transferência de Genes
, Compostos de Amônio Quaternário/química
, Tensoativos/química
, Transfecção/métodos
, DNA/química
, DNA/genética
, Eletroporação
, Proteínas de Fluorescência Verde/genética
, Proteínas de Fluorescência Verde/metabolismo
, Células HEK293
, Humanos
, Microscopia de Força Atômica
, Estrutura Molecular
, Conformação de Ácido Nucleico
, Plasmídeos/química
, Plasmídeos/genética
, Reprodutibilidade dos Testes
, Relação Estrutura-Atividade
, Termodinâmica
RESUMO
Adsorption of fibrinogen on the luminal surface of biomaterials is a critical early event during the interaction of blood with implanted vascular graft prostheses which determines their thrombogenicity. We have recently identified a nanoscale process by which fibrinogen modifies the adhesive properties of various surfaces for platelets and leukocytes. In particular, adsorption of fibrinogen at low density promotes cell adhesion while its adsorption at high density results in the formation of an extensible multilayer matrix, which dramatically reduces cell adhesion. It remains unknown whether deposition of fibrinogen on the surface of vascular graft materials produces this anti-adhesive effect. Using atomic force spectroscopy, single cell force spectroscopy, and standard adhesion assays with platelets and leukocytes, we have characterized the adhesive and physical properties of the contemporary biomaterials, before and after coating with fibrinogen. We found that uncoated PET, PTFE and ePTFE exhibited high adhesion forces developed between the AFM tip or cells and the surfaces. Adsorption of fibrinogen at the increasing concentrations progressively reduced adhesion forces, and at ≥2 µg/ml all surfaces were virtually nonadhesive. Standard adhesion assays performed with platelets and leukocytes confirmed this dependence. These results provide a better understanding of the molecular events underlying thrombogenicity of vascular grafts.