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1.
J Phys Chem B ; 128(14): 3329-3339, 2024 Apr 11.
Artigo em Inglês | MEDLINE | ID: mdl-38557033

RESUMO

In nature, DNA exists primarily in a highly compacted form. The compaction of DNA in vivo is mediated by cationic proteins: histones in somatic nuclei and protamines in sperm chromatin. The extreme, nearly crystalline packaging of DNA by protamines in spermatozoa is thought to be essential for both efficient genetic delivery as well as DNA protection against damage by mutagens and oxidative species. The protective role of protamines is required in sperm, as they are sensitive to ROS damage due to the progressive loss of DNA repair mechanisms during maturation. The degree to which DNA packaging directly relates to DNA protection in the condensed state, however, is poorly understood. Here, we utilized different polycation condensing agents to achieve varying DNA packaging densities and quantify DNA damage by free radical oxidation within the condensates. Although we see that tighter DNA packaging generally leads to better protection, the length of the polycation also plays a significant role. Molecular dynamics simulations suggest that longer polyarginine chains offer increased protection by occupying more space on the DNA surface and forming more stable interactions. Taken together, our results suggest a complex interplay among polycation properties, DNA packaging density, and DNA protection against free radical damage within condensed states.


Assuntos
DNA , Polieletrólitos , Sêmen , Masculino , Humanos , DNA/química , Cromatina , Protaminas/química , Espermatozoides , Empacotamento do DNA , Dano ao DNA
2.
J Chromatogr A ; 1721: 464861, 2024 Apr 26.
Artigo em Inglês | MEDLINE | ID: mdl-38564931

RESUMO

The covalent attachment of polyoxometalates (POMs) to polymers has been developed as a strategic approach for the advancement of POM-based hybrid materials with versatile applications. In this study, we utilized thiol-maleimide Michael addition to investigate the kinetics and efficacy of the "one-to-one" conjugation between Keggin type POM and polystyrene. We explored the effects of solvent polarity, catalyst, molecular weight of PS and synthetic strategies on the reaction kinetics and efficiency, by means of reverse-phase high-performance liquid chromatography (RP-HPLC). A series of comparative analysis affirmed the superior efficiency of the one-pot method, particularly when facilitated by the addition of a high-polarity solvent and an excess of maleimide. These findings offer valuable insights into the intricate interplay between reaction conditions, kinetics, and selectivity in thiol-maleimide reactions of POMs and polymers. They hold profound implications for advancing the study of POM-based multifunctional materials and the synthesis of complex hybrid molecules.


Assuntos
Ânions , Polieletrólitos , Polímeros , Compostos de Sulfidrila , Polímeros/química , Maleimidas/química , Solventes
3.
ACS Nano ; 18(15): 10427-10438, 2024 Apr 16.
Artigo em Inglês | MEDLINE | ID: mdl-38556978

RESUMO

Protein translocation through nanopores holds significant promise for applications in biotechnology, biomolecular analysis, and medicine. However, the interpretation of signals generated by the translocation of the protein remains challenging. In this way, it is crucial to gain a comprehensive understanding on how macromolecules translocate through a nanopore and to identify what are the critical parameters that govern the process. In this study, we investigate the interplay between protein charge regulation, orientation, and nanopore surface modifications using a theoretical framework that allows us to explicitly take into account the acid-base reactions of the titrable amino acids in the proteins and in the polyelectrolytes grafted to the nanopore surface. Our goal is to thoroughly characterize the translocation process of different proteins (GFP, ß-lactoglobulin, lysozyme, and RNase) through nanopores modified with weak polyacids. Our calculations show that the charge regulation mechanism exerts a profound effect on the translocation process. The pH-dependent interactions between proteins and charged polymers within the nanopore lead to diverse free energy landscapes with barriers, wells, and flat regions dictating translocation efficiency. Comparison of different proteins allows us to identify the significance of protein isoelectric point, size, and morphology in the translocation behavior. Taking advantage of these insights, we propose pH-responsive nanopores that can load proteins at one pH and release them at another, offering opportunities for controlled protein delivery, separation, and sensing applications.


Assuntos
Nanoporos , Polímeros/química , Polieletrólitos , Proteínas/química , Transporte Proteico
4.
Soft Matter ; 20(16): 3499-3507, 2024 Apr 24.
Artigo em Inglês | MEDLINE | ID: mdl-38595066

RESUMO

Polymeric vesicles are perspective vehicles for fabricating enzymatic nanoreactors towards diverse biomedical and catalytic applications, yet the design of stable and permeable vesicles remains challenging. Herein, we developed polyion complex (PIC) vesicles featuring high stability and a permeable membrane for adequate enzyme loading and activation. Our design relies on co-assembly of an anionic diblock copolymer (PSS96-b-PEO113) with cationic branched poly(ethylenimine) (PEI). The polymer combination endows strong electrostatic interaction between the PSS and PEI building blocks, so their assembly can be implemented at a high salt concentration (500 mM NaCl), under which the charge interaction of the enzyme-polymer is inhibited. This control realizes the successful and safe loading of enzymes associated with the formation of stable PIC vesicles with an intrinsic permeable membrane that is favourable for enhancing enzymatic activity. The control factors for vesicle formation and enzyme loading were investigated, and the general application of loading different enzymes for cascade reaction was validated as well. Our study reveals that proper design and combination of polyelectrolytes is a facile strategy for fabricating stable and permeable polymeric PIC vesicles, which exhibit clear advantages for loading and activating enzymes, consequently boosting their diverse applications as enzymatic nanoreactors.


Assuntos
Polietilenoimina , Polietilenoimina/química , Permeabilidade , Polímeros/química , Polieletrólitos/química
5.
J Chromatogr A ; 1720: 464802, 2024 Apr 12.
Artigo em Inglês | MEDLINE | ID: mdl-38507871

RESUMO

Successive multiple ionic-polymer layers (SMILs) have long since proved their worth in capillary electrophoresis as they ensure stable electroosmotic flow (EOF) and relatively high separation efficiency. Recently, we demonstrated that plotting the plate height (H) against the solute migration velocity (u) enabled a reliable quantitative evaluation of the coating performances in terms of separation efficiency. In this work, various physicochemical and chemical parameters of the SMIL coating were studied and optimized in order to decrease the slope of the ascending part of the H vs u curve, which is known to be controlled by the homogeneity in charge of the coating surface and by the possible residual solute adsorption onto the coating surface. SMILs based on poly(diallyldimethylammonium chloride) (PDADMAC) and poly(sodium styrene sulfonate) (PSS) were formed and the effect of each polyelectrolyte molar mass and of the number of polyelectrolyte layers (up to 21 layers) was studied. The use of polyethylene imine as an anchoring first layer was considered. More polyelectrolyte couples based on PDADMAC, polybrene, PSS, poly(vinyl sulfate), and poly(acrylic acid) were tested. Finally, zwitterionic polymers based on the poly(α-l-lysine) scaffold were synthesized and used as the last layer of SMILs, illustrating their ability to finetune the EOF, while maintaining good separation efficiency.


Assuntos
Eletroforese Capilar , Polietilenos , Polímeros , Compostos de Amônio Quaternário , Polieletrólitos , Cátions , Eletroforese Capilar/métodos , Proteínas/análise , Polietilenoimina
6.
Methods Appl Fluoresc ; 12(3)2024 Apr 05.
Artigo em Inglês | MEDLINE | ID: mdl-38537290

RESUMO

Polycationic photosensitizers (PS) are not susceptible to aggregation in solutions, but their high local concentrations in Gram-negative bacteria can be sufficient for aggregation and reduced effectiveness of antibacterial photodynamic treatment. By measuring fluorescence spectra and kinetics we were able to evaluate the degree of aggregation of polycationic PS ZnPcChol8in Gram-negative bacteria E.coliK12 TG1. Binding of ZnPcChol8toE.coliK12 TG1 leads to an appearance of groups of molecules with shorter PS fluorescence lifetime, a decrease in fluorescence intensity and a shift in the fluorescence spectral maximum. However, we evaluated that about 88% of the fluorescing PS molecules in the bacteria were in an unaggregated state, which indicates only a small reduction in the generation of reactive oxygen species.


Assuntos
Fotoquimioterapia , Fármacos Fotossensibilizantes , Polieletrólitos , Fármacos Fotossensibilizantes/farmacologia , Fármacos Fotossensibilizantes/química , Bactérias Gram-Negativas/metabolismo , Espécies Reativas de Oxigênio/metabolismo
7.
Langmuir ; 40(14): 7300-7309, 2024 Apr 09.
Artigo em Inglês | MEDLINE | ID: mdl-38536237

RESUMO

DNA sequencing and sensing using nanopore technology delves critically into the alterations in the measurable electrical signal as single-stranded DNA is drawn through a tiny passage. To make such precise measurements, however, slowing down the DNA in the tightly confined passage is a key requirement, which may be achieved by grafting the nanopore walls with a polyelectrolyte layer (PEL). This soft functional layer at the wall, under an off-design condition, however, may block the DNA passage completely, leading to the complete loss of output signal from the nanobio sensor. Whereas theoretical postulates have previously been put forward to explain the essential physics of DNA translocation in nanopores, these have turned out to be somewhat inadequate when confronted with the experimental findings on functionalized nanopores, including the prediction of the events of complete signal losses. Circumventing these constraints, herein we bring out a possible decisive role of the interplay between the inevitable variabilities in the ionic distribution along the nanopore axis due to its finite length as opposed to its idealized "infinite" limit as well as the differential permittivity of PEL and bulk solution that cannot be captured by the commonly used one-dimensional variant of the electrical double layer theory. Our analysis, for the first time, captures variations in the ionic concentration distribution across multidimensional physical space and delineates its impact on the DNA translocation characteristics that have hitherto remained unaddressed. Our results reveal possible complete blockages of DNA translocation as influenced by less-than-threshold permittivity values or greater-than-threshold grafting densities of the PEL. In addition, electrohydrodynamic blocking is witnessed due to the ion-selective nature of the nanopore at low ionic concentrations. Hence, our study establishes a functionally active regime over which the PEL layer in a finite-length nanopore facilitates controllable DNA translocation, enabling successful sequencing and sensing through the explicit modulation of translocation speed.


Assuntos
Nanoporos , Polieletrólitos , DNA , DNA de Cadeia Simples , Íons
8.
Int J Biol Macromol ; 264(Pt 2): 130787, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38548499

RESUMO

In present study, polysaccharide polyelectrolyte nanoparticles (CMAAP-CS NPs) were constructed by mixing carboxymethylated Anemarrhena asphodeloides polysaccharide (CMAAP) and chitosan (CS). CMAAP-CS NPs were applied as carrier to improve the bioavailability and stability of curcumin (Cur). The average particle size of CMAAP-CS NPs was 216.60 ± 4.21 nm and the entrapment efficiency of Cur reached 82.50 ± 2.09 %. The simulated digestion experiments in vitro confirmed that the bioavailability of Cur loaded in CMAAP-CS NPs was 59.84 ± 0.03 % after saliva, gastric and intestinal digestion, which was obvious higher than 21.57 ± 0.07 % of free Cur under the same conditions. The results of stability testing revealed that CMAAP-CS NPs could markedly reduce the degradation of Cur against storage, heating, UV light treatment, and neutral pH. This study provided promising polyelectrolyte complex loaded hydrophobic nutrients in medicine industry.


Assuntos
Anemarrhena , Quitosana , Curcumina , Nanopartículas , Curcumina/química , Portadores de Fármacos/química , Quitosana/química , Polieletrólitos , Polissacarídeos/farmacologia , Nanopartículas/química , Antibacterianos/farmacologia , Tamanho da Partícula
9.
ACS Appl Bio Mater ; 7(4): 2544-2553, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38507285

RESUMO

The poor accumulation of antibiotics in the cytoplasm leads to the poor eradication of intracellular bacteria. Herein, a polyelectrolyte complex (PECs@Rif) allowing direct cytosolic delivery of rifampicin (Rif) was developed for the treatment of intracellular infections by complexation of poly(α-lipoic acid) (pLA) and oligosaccharide (COS) in water and loading Rif. Due to the thiol-mediated cellular uptake, PECs@Rif delivered 3.9 times higher Rif into the cytoplasm than that of the free Rif during 8 h of incubation. After entering cells, PECs@Rif released Rif by dissociating pLA into dihydrolipoic acid (DHLA) in the presence of intracellular thioredoxin reductase (TrxR). Notably, DHLA could reduce endogenous Fe(III) to Fe(II) and provide a catalyst for the Fenton reaction to produce a large amount of reactive oxygen species (ROS), which would assist Rif in eradicating intracellular bacteria. In vitro assay showed that PECs@Rif reduced almost 2.8 orders of magnitude of intracellular bacteria, much higher than 0.7 orders of magnitude of free Rif. The bacteremia-bearing mouse models showed that PECs@Rif reduced bacterial levels in the liver, spleen, and kidney by 2.2, 3.7, and 2.3 orders of magnitude, respectively, much higher than free Rif in corresponding tissues. The direct cytosolic delivery in a thiol-mediated manner and enhanced oxidative stress proposed a feasible strategy for treating intracellular bacteria infection.


Assuntos
Compostos Férricos , Rifampina , Camundongos , Animais , Rifampina/farmacologia , Polieletrólitos , Estresse Oxidativo , Bactérias
10.
Adv Colloid Interface Sci ; 326: 103133, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38547652

RESUMO

DNA is a highly charged polyelectrolyte and is prone to associative phase separation driven by the presence of multivalent cations, charged surfactants, proteins, polymers and colloids. The process of DNA phase separation induced by positively charged species is often called DNA condensation. Generally, it refers to either intramolecular DNA compaction (coil-globule transition) or intermolecular DNA aggregation with macroscopic phase separation, but the formation of a DNA liquid crystalline system is also displayed. This has traditionally been described by polyelectrolyte theory and qualitative (Flory-Huggins-based) polymer theory approaches. DNA in the cell nucleus is packed into chromatin wound around the histone octamer (a protein complex comprising two copies each of the four histone proteins H2A, H2B, H3 and H4) to form nucleosomes separated by linker DNA. During the last decade, the phenomenon of the formation of biomolecular condensates (dynamic droplets) by liquid-liquid phase separation (LLPS) has emerged as a generally important mechanism for the formation of membraneless organelles from proteins, nucleic acids and their complexes. DNA and chromatin droplet formation through LLPS has recently received much attention by in vitro as well as in vivo studies that established the importance of this for compartmentalisation in the cell nucleus. Here, we review DNA and chromatin LLPS from a general colloid physical chemistry perspective. We start with a general discussion of colloidal phase separation in aqueous solutions and review the original (pre-LLPS era) work on DNA (macroscopic) phase separation for simpler systems with DNA in the presence of multivalent cations and well-defined surfactants and colloids. Following that, we discuss and illustrate the similarities of such macroscopic phase separation with the general behaviour of LLPS droplet formation by associative phase separation for DNA-protein systems, including chromatin; we also note cases of segregative association. The review ends with a discussion of chromatin LLPS in vivo and its physiological significance.


Assuntos
Cromatina , Histonas , Histonas/metabolismo , Polieletrólitos , 60422 , DNA , Polímeros/metabolismo , Físico-Química , Coloides , Cátions/metabolismo , Tensoativos
11.
J Colloid Interface Sci ; 665: 801-813, 2024 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-38555748

RESUMO

The co-assembly of polyelectrolytes (PE) with proteins offers a promising approach for designing complex structures with customizable morphologies, charge distribution, and stability for targeted cargo delivery. However, the complexity of protein structure limits our ability to predict the properties of the formed nanoparticles, and our goal is to identify the key triggers of the morphological transition in protein/PE complexes and evaluate their ability to encapsulate multivalent ionic drugs. A positively charged PE can assemble with a protein at pH above isoelectric point due to the electrostatic attraction and disassemble at pH below isoelectric point due to the repulsion. The additional hydrophilic block of the polymer should stabilize the particles in solution and enable them to encapsulate a negatively charged drug in the presence of PE excess. We demonstrated that diblock copolymers, poly(ethylene oxide)-block-poly(N,N-dimethylaminoethyl methacrylate) and poly(ethylene oxide)-block-poly(N,N,N-trimethylammonioethyl methacrylate), consisting of a polycation block and a neutral hydrophilic block, reversibly co-assemble with insulin in pH range between 5 and 8. Using small-angle neutron and X-ray scattering (SANS, SAXS), we showed that insulin arrangement within formed particles is controlled by intermolecular electrostatic forces between protein molecules, and can be tuned by varying ionic strength. For the first time, we observed by fluorescence that formed protein/PE complexes with excess of positive charges exhibited potential for encapsulating and controlled release of negatively charged bivalent drugs, protoporphyrin-IX and zinc(II) protoporphyrin-IX, enabling the development of nanocarriers for combination therapies with adjustable charge, stability, internal structure, and size.


Assuntos
Insulina , Protoporfirinas , Polieletrólitos , Óxido de Etileno , Espalhamento a Baixo Ângulo , Difração de Raios X , Polímeros/química , Proteínas , Ponto Isoelétrico
12.
Int J Biol Macromol ; 264(Pt 1): 130457, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38432265

RESUMO

A mucoadhesive polyelectrolyte complex (PEC) nanoparticles were developed for ocular moxifloxacin (Mox) delivery in Bacterial Keratitis (BK). Moxifloxacin-loaded G/CG-Alg NPs were prepared by an amalgamation of cationic polymers (gelatin (G)/cationized gelatin (CG)), and anionic polymer (sodium alginate (Alg)) along with Mox respectively. Mox@CG-Alg NPs were characterized for physicochemical parameters such as particle size (DLS technique), morphology (SEM analysis), DSC, XRD, encapsulation efficiency, drug loading, mucoadhesive study (by texture analyzer), mucin turbidity, and viscosity assessment. The NPs uptake and toxicity of the formulation were analyzed in the Human Corneal Epithelial (HCE) cell line and an ocular irritation study was performed on the HET-CAM. The results indicated that the CG-Alg NPs, with optimal size (217.2 ± 4 nm) and polydispersity (0.22 ± 0.05), have shown high cellular uptake in monolayer and spheroids of HCE. The drug-loaded formulation displayed mucoadhesiveness, trans-corneal permeation, and sustained the release of the Mox. The anti-bacterial efficacy studied on planktonic bacteria/biofilms of P. aeruginosa and S. aureus (in vitro) indicated that the Mox@CG-Alg NPs displayed low MIC, higher zone of bacterial growth inhibition, and cell death compared to free Mox. A significant reduction of bacterial load was observed in the BK-induced mouse model.


Assuntos
Dieldrin/análogos & derivados , Infecções Oculares Bacterianas , Ceratite , Nanopartículas , Camundongos , Animais , Humanos , Moxifloxacina/farmacologia , Gelatina/química , Polieletrólitos , Alginatos/química , Staphylococcus aureus , Soluções Oftálmicas , Nanopartículas/química , Ceratite/tratamento farmacológico
13.
Proc Natl Acad Sci U S A ; 121(11): e2307809121, 2024 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-38437543

RESUMO

Rapid advances in nucleic acid therapies highlight the immense therapeutic potential of genetic therapeutics. Lipid nanoparticles (LNPs) are highly potent nonviral transfection agents that can encapsulate and deliver various nucleic acid therapeutics, including but not limited to messenger RNA (mRNA), silencing RNA (siRNA), and plasmid DNA (pDNA). However, a major challenge of targeted LNP-mediated systemic delivery is the nanoparticles' nonspecific uptake by the liver and the mononuclear phagocytic system, due partly to the adsorption of endogenous serum proteins onto LNP surfaces. Tunable LNP surface chemistries may enable efficacious delivery across a range of organs and cell types. Here, we describe a method to electrostatically adsorb bioactive polyelectrolytes onto LNPs to create layered LNPs (LLNPs). LNP cores varying in nucleic acid cargo and component lipids were stably layered with four biologically relevant polyanions: hyaluronate (HA), poly-L-aspartate (PLD), poly-L-glutamate (PLE), and polyacrylate (PAA). We further investigated the impact of the four surface polyanions on the transfection and uptake of mRNA- and pDNA-loaded LNPs in cell cultures. PLD- and PLE-LLNPs increased mRNA transfection twofold over unlayered LNPs in immune cells. HA-LLNPs increased pDNA transfection rates by more than twofold in epithelial and immune cells. In a healthy C57BL/6 murine model, PLE- and HA-LLNPs increased transfection by 1.8-fold to 2.5-fold over unlayered LNPs in the liver and spleen. These results suggest that LbL assembly is a generalizable, highly tunable platform to modify the targeting specificity, stability, and transfection efficacy of LNPs, as well as incorporate other charged targeting and therapeutic molecules into these systems.


Assuntos
Lipossomos , Nanopartículas , Animais , Camundongos , Polieletrólitos , Adsorção , Eletricidade Estática , Transfecção , RNA Mensageiro/genética , RNA Interferente Pequeno/genética , Ácido Glutâmico
14.
Phys Chem Chem Phys ; 26(11): 8873-8878, 2024 Mar 13.
Artigo em Inglês | MEDLINE | ID: mdl-38426343

RESUMO

Understanding polycation-lipid interaction is essential not only in molecular biology but also in the biomedical industry and pharmacology. However, the effect of the polycation-lipid interaction on the molecular properties of lipids in biomembranes remains elusive. Here, two fluorescence correlation spectroscopies (FCSs), pulse-interleaved excitation (PIE) FCS and lifetime-based FCS, were performed to elucidate the change in the lipid diffusion of a model biomembrane induced by polylysine (PLL) adsorption. The results of PIE-FCS showed that the diffusions of both anionic and zwitterionic lipids become slower in the presence of PLL but the mobility of the anionic lipids is much reduced, suggesting the preferential interaction between the PLL and the anionic lipids due to the electrostatic attraction. Furthermore, leaflet-specific lipid diffusion analysis by lifetime-based FCS clearly showed that PLL adsorption on one leaflet of the membrane reduces the lipid diffusion of both leaflets in the same manner. This clearly indicates that the interleaflet coupling is strong in the presence of PLL.


Assuntos
Bicamadas Lipídicas , Polieletrólitos , Polilisina , Adsorção , Difusão
15.
Int J Mol Sci ; 25(5)2024 Feb 22.
Artigo em Inglês | MEDLINE | ID: mdl-38473818

RESUMO

Polyoxotungstate nanoclusters have recently emerged as promising contrast agents for computed tomography (CT). In order to evaluate their clinical potential, in this study, we evaluated the in vitro CT imaging properties, potential toxic effects in vivo, and tissue distribution of monolacunary Wells-Dawson polyoxometalate, α2-K10P2W17O61.20H2O (mono-WD POM). Mono-WD POM showed superior X-ray attenuation compared to other tungsten-containing nanoclusters (its parent WD-POM and Keggin POM) and the standard iodine-based contrast agent (iohexol). The calculated X-ray attenuation linear slope for mono-WD POM was significantly higher compared to parent WD-POM, Keggin POM, and iohexol (5.97 ± 0.14 vs. 4.84 ± 0.05, 4.55 ± 0.16, and 4.30 ± 0.09, respectively). Acute oral (maximum-administered dose (MAD) = 960 mg/kg) and intravenous administration (1/10, 1/5, and 1/3 MAD) of mono-WD POM did not induce unexpected changes in rats' general habits or mortality. Results of blood gas analysis, CO-oximetry status, and the levels of electrolytes, glucose, lactate, creatinine, and BUN demonstrated a dose-dependent tendency 14 days after intravenous administration of mono-WD POM. The most significant differences compared to the control were observed for 1/3 MAD, being approximately seventy times higher than the typically used dose (0.015 mmol W/kg) of tungsten-based contrast agents. The highest tungsten deposition was found in the kidney (1/3 MAD-0.67 ± 0.12; 1/5 MAD-0.59 ± 0.07; 1/10 MAD-0.54 ± 0.05), which corresponded to detected morphological irregularities, electrolyte imbalance, and increased BUN levels.


Assuntos
Ânions , Meios de Contraste , Iohexol , Polieletrólitos , Ratos , Animais , Distribuição Tecidual , Tungstênio , Tomografia Computadorizada por Raios X
16.
Int J Mol Sci ; 25(5)2024 Feb 24.
Artigo em Inglês | MEDLINE | ID: mdl-38473899

RESUMO

Allapinin has antiarrhythmic activity and can be used to prevent and treat various supraventricular and ventricular arrhythmias. Nevertheless, it is highly toxic and has a number of side effects associated with non-specific accumulation in various tissues. The complex of this substance with the monoammonium salt of glycyrrhizic acid (Al:MASGA) has less toxicity and improved antiarrhythmic activity. However, the encapsulation of Al:MASGA in polyelectrolyte microcapsules (PMC) for prolonged release will reduce the residual adverse effects of this drug. In this work, the possibility of encapsulating the allapinin-MASGA complex in polyelectrolyte microcapsules based on polyallylamine and polystyrene sulfonate was investigated. The encapsulation methods of the allapinin-MASGA in polyelectrolyte microcapsules by adsorption and coprecipitation were compared. It was found that the coprecipitation method did not result in the encapsulation of Al:MASGA. The sorption method facilitated the encapsulation of up to 80% of the original substance content in solution in PMC. The release of the encapsulated substance was further investigated, and it was shown that the release of the encapsulated Al:MASGA was independent of the substance content in the capsules, but at pH 5, a two-fold decrease in the rate of drug release was observed.


Assuntos
Aconitina/análogos & derivados , Ácido Glicirrízico , Cloreto de Sódio , Polieletrólitos , Cápsulas/química , Cloreto de Sódio na Dieta
17.
J Chromatogr A ; 1718: 464719, 2024 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-38340458

RESUMO

Dendrigraft poly(L-lysine) (DGL) constitutes a promising dendritic-like drug vehicle with high biocompatibility and straightforward access via ring-opening polymerization of N-carboxyanhydride in water. The characterization of the different generations of DGL is however challenging due to their heterogeneity in molar mass and branching ratio. In this work, free solution capillary electrophoresis was used to perform selective separation of the three first generations of DGL, and optimized conditions were developed to maximize inter-generation resolution. To reduce solute adsorption on the capillary wall, successive multiple ionic polymer layer coatings terminated with a polycation were deposited onto the inner wall surface. PEGylated polycation was also used as the last layer for the control of the electroosmotic flow (EOF), depending on the PEGylation degree and the methyl-polyethylene glycol (mPEG) chain length. 1 kDa mPEG chains and low grafting densities were found to be the best experimental conditions for a fine tuning of the EOF leading to high peak resolution. Molar mass polydispersity and polydispersity in effective electrophoretic mobility were successfully determined for the three first generations of DGL.


Assuntos
Polietilenoglicóis , Polietilenos , Polilisina , Polieletrólitos , Eletroforese Capilar/métodos
18.
Int J Biol Macromol ; 264(Pt 1): 130384, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38395282

RESUMO

The present work describes the process of degradation of a polyelectrolytic complex (PEC) based on sodium alginate (ALG) and chitosan (CHI), buried for different time intervals, in a clayey soil (ultisol) collected from the municipality of Campos dos Goytacazes, in the northern region of the state of Rio de Janeiro, Brazil. The influence of PEC on soil moisture was also investigated. The results showed that soil moisture increased with the presence of PEC after 7 days of testing, and remained high until the end of the study. FTIR and Raman spectra showed that the breaking of the glycosidic bond (C-O-C) was responsible for the PEC degradation. Thermogravimetry results revealed that alginate was possibly degraded faster than chitosan. Microscopic analysis of the PEC revealed a fragile and fragmented surface of the samples that were buried, in comparison with those not buried. The microbiological assays of the soil confirmed the biodegradation of the polysaccharides. Chemical analysis of soil indicated that PEC did not significantly influence soil fertility. Therefore, we conclude that the PEC (ALG: CHI), formed only by electrostatic interaction, buried in clayey soil, even being biodegraded, can be a promising soil conditioner for agricultural applications.


Assuntos
Quitosana , Quitosana/química , Alginatos/química , Solo , Brasil , Polieletrólitos/química
19.
Int J Biol Macromol ; 264(Pt 1): 130445, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38423441

RESUMO

Biopolymer-derived polyelectrolyte complexes (PECs) are a class of materials that have emerged as promising candidates for developing advanced electrochemical sensors due to their tunable properties, biocompatibility, cost-effective production, and high surface area. PECs are formed by combining positively and negatively charged polymers, resulting in a network with intriguing properties that can be tailored for specific sensing applications. The resultant PECs-based nanocomposites were used to modify the glassy carbon electrode (GCE) to detect the sulfamethazine (SFZ) antibiotic drug. In addition, electrochemical studies using electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and differential pulse voltammetry (DPV) are used to evaluate the SFZ detection ability. Similarly, various microscopic and spectroscopic studies investigated the nano composite's structural features and morphological behavior. The κ-CGN/P(Am-co-DMDAAc)-GO modified GCE demonstrated excellent detection ability of SFZ with the nano molar range and without interference with similar structural components. Furthermore, the newly fabricated electrode κ-CGN/P(Am-co-DMDAAc)-GO was derived from naturally available materials, water-soluble, low cost, biocompatible, exhibits good conductivity, and excellent catalytic properties. Finally, κ-CGN/P(Am-co-DMDAAc)-GO- modified GCE has versatile, practical applications for detecting SFZ in real-time samples and determining the efficacy of an antibacterial activity.


Assuntos
Técnicas Eletroquímicas , Sulfametazina , Polieletrólitos , Carragenina , Técnicas Eletroquímicas/métodos , Antibacterianos/farmacologia , Carbono/química
20.
Int J Biol Macromol ; 263(Pt 2): 130282, 2024 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-38423901

RESUMO

Aiming at green and friendly environmental protection, polyvinyl alcohol/sodium alginate/chitosan (PSCS) double network hydrogel was successfully prepared through diffusing the high molecular weight chitosan into PVA/sodium alginate (PS) hydrogel without any other toxic reagents. The polyanion hydrogels could be significantly enhanced by immersing the polyanion hydrogel in high molecular weight chitosan solution without requiring specific structure. The PSCS hydrogel had a compact and rough surface structure with the smaller porosities and larger crystallization degree compared with polyvinyl alcohol/sodium alginate hydrogels and polyvinyl alcohol/sodium alginate/Ca2+ (PSCa) hydrogels. The PSCS hydrogel possessed excellent hydrolysis resistance, the significant pH-sensitive and salt-sensitive swelling. In addition, the flexibility, Young's modulus and mechanical properties of PSCS hydrogel can be adjusted through the changing the content of sodium alginate. Moreover, PS, PSCa and PSCS had electric conductivity, and PSCS showed twice the conductivity compared to PS hydrogel. Based on differences of swelling ratio, a PSCS bilayer hydrogel was designed and showed excellent pH-driven deformation ability. The PSCS hydrogel is expected to expand the application of hydrogels in conditions involving stimulus response, and might serve as a promising intelligent actuators or soft robots.


Assuntos
Quitosana , Polieletrólitos , Quitosana/química , Álcool de Polivinil/química , Hidrogéis/química , Alginatos/química , Concentração de Íons de Hidrogênio , Condutividade Elétrica
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