Probing Surface Transformations of Lanthanum Nickelate Electrocatalysts during Oxygen Evolution Reaction.

Monitoring the spontaneous reconstruction of the surface of metal oxides under electrocatalytic reaction conditions is critical to identifying the active sites and establishing structure-activity relationships. Here, we report on a self-terminated surface reconstruction of Ruddlesden-Popper lanthanum nickel oxide (La2NiO4+δ) that occurs spontaneously during reaction with alkaline electrolyte species. Using a combination of high-resolution scanning transmission electron microscopy (HR-STEM), surface-sensitive X-ray photoelectron spectroscopy (XPS), and soft X-ray absorption spectroscopy (sXAS), as well as electrochemical techniques, we identify the structure of the reconstructed surface layer as an amorphous (oxy)hydroxide phase that features abundant under-coordinated nickel sites. No further amorphization of the crystalline oxide lattice (beyond the ∼2 nm thick layer formed) was observed during oxygen evolution reaction (OER) cycling experiments. Notably, the formation of the reconstructed surface layer increases the material's oxygen evolution reaction (OER) activity by a factor of 45 when compared to that of the pristine crystalline surface. In contrast, a related perovskite phase, i.e., LaNiO3, did not show noticeable surface reconstruction, and also no increase in its OER activity was observed. This work provides detailed insight into a surface reconstruction behavior dictated by the crystal structure of the parent oxide and highlights the importance of surface dynamics under reaction conditions.

Piperidinium surfactants functionalized with carbamate fragment: Aggregation, antimicrobial activity and cytotoxicity.

The biomimetic nature of supramolecular systems, the structural similarity of synthetic surfactants to biomolecules (lipids, proteins), provide them with high membranotropy, the ability to overcome biological barriers, and affinity towards biosubstances. Despite rather high toxicity cationic surfactants are of importance as antimicrobial agents, gene nanocarriers and mitochondria targeted ligands. To minimize this limitation, cationic amphiphilic matrix undergoes modification with various functional groups. In this work, new piperidinium cationic surfactants containing one or two carbamate fragments were prepared; their aggregation behavior was systematically studied by tensiometery, spectrophotometry and fluorimetry. The presence of a carbamate fragment leads to a 2-3-fold decrease in critical micelle concentration and to a significant increase in solubilization capacity compared to unsubstituted analogue. Evaluation of the antimicrobial effect showed that all compounds exhibit high bactericidal and fungicidal activity against a wide range of pathogenic microorganisms, including their resistant forms. Importantly, the introducing carbamate moiety allows of decreasing hemolytic activity of cationic surfactants. The data obtained make it possible to recommend carbamate piperidinium surfactants as effective biocompatible and biodegradable nanocontainers for hydrophobic probes with high antimicrobial effect and moderate hemolytic activity.

A case of vitiligo after COVID-19 vaccination: a possible role of thymic dysfunction. / 一例由2019å† ç— æ¯’ç— (COVID-19)ç–«è‹—æŽ¥ç§å¼•å‘çš„ç™½ç™œé£Žç— ä¾‹åŠå ¶èƒ¸è ºåŠŸèƒ½éšœç¢çš„ä½œç”¨æœºåˆ¶åˆ†æž.

During the coronavirus disease 2019 (COVID-19) pandemic, vaccines help control the spread of infection. To date, 47 vaccines have been approved, with another 227 candidates in various stages of development. In the short period of time since the beginning of their use, evidence has begun to emerge of complications following vaccination in the form of the development or exacerbation of a number of pathological conditions (Block et al., 2022; Haseeb et al., 2022). For example, a population-based study in France identified 1612 cases of myocarditis and 1613 cases of pericarditis requiring hospital treatment within five months of vaccination (le Vu et al., 2022).

Understanding the Synergy between Fe and Mo Sites in the Nitrate Reduction Reaction on a Bio-Inspired Bimetallic MXene Electrocatalyst.

Mo- and Fe-containing enzymes catalyze the reduction of nitrate and nitrite ions in nature. Inspired by this activity, we study here the nitrate reduction reaction (NO3 RR) catalyzed by an Fe-substituted two-dimensional molybdenum carbide of the MXene family, viz., Mo2 CTx : Fe (Tx are oxo, hydroxy and fluoro surface termination groups). Mo2 CTx : Fe contains isolated Fe sites in Mo positions of the host MXene (Mo2 CTx ) and features a Faradaic efficiency (FE) and an NH3 yield rate of 41 % and 3.2 µmol h-1 mg-1 , respectively, for the reduction of NO3 - to NH4 + in acidic media and 70 % and 12.9 µmol h-1 mg-1 in neutral media. Regardless of the media, Mo2 CTx : Fe outperforms monometallic Mo2 CTx owing to a more facile reductive defunctionalization of Tx groups, as evidenced by in situ X-ray absorption spectroscopy (Mo K-edge). After surface reduction, a Tx vacancy site binds a nitrate ion that subsequently fills the vacancy site with O* via oxygen transfer. Density function theory calculations provide further evidence that Fe sites promote the formation of surface O vacancies, which are identified as active sites and that function in NO3 RR in close analogy to the prevailing mechanism of the natural Mo-based nitrate reductase enzymes.

Synthesis, Properties, and Biomedical Application of Dicationic Gemini Surfactants with Dodecane Spacer and Carbamate Fragments.

A synthesis procedure and aggregation properties of a new homologous series of dicationic gemini surfactants with a dodecane spacer and two carbamate fragments (N,N'-dialkyl-N,N'-bis(2-(ethylcarbamoyloxy)ethyl)-N,N'-dimethyldodecan-1,6-diammonium dibromide, n-12-n(Et), where n = 10, 12, 14) were comprehensively described. The critical micelle concentrations of gemini surfactants were obtained using tensiometry, conductometry, spectrophotometry, and fluorimetry. The thermodynamic parameters of adsorption and micellization, i.e., maximum surface excess (Гmax), the surface area per surfactant molecule (Amin), degree of counterion binding (ß), and Gibbs free energy of micellization (∆Gmic), were calculated. Functional activity of the surfactants, including the solubilizing capacity toward Orange OT and indomethacin, incorporation into the lipid bilayer, minimum inhibitory concentration, and minimum bactericidal and fungicidal concentrations, was determined. Synthesized gemini surfactants were further used for the modification of liposomes dual-loaded with α-tocopherol and donepezil hydrochloride for intranasal treatment of Alzheimer's disease. The obtained liposomes have high stability (more than 5 months), a significant positive charge (approximately + 40 mV), and a high degree of encapsulation efficiency toward rhodamine B, α-tocopherol, and donepezil hydrochloride. Korsmeyer-Peppas, Higuchi, and first-order kinetic models were used to process the in vitro release curves of donepezil hydrochloride. Intranasal administration of liposomes loaded with α-tocopherol and donepezil hydrochloride for 21 days prevented memory impairment and decreased the number of Aß plaques by 37.6%, 40.5%, and 72.6% in the entorhinal cortex, DG, and CA1 areas of the hippocampus of the brain of transgenic mice with Alzheimer's disease model (APP/PS1) compared with untreated animals.

Structural Features and Water Resistance of Glass-Matrix Composites in a System of RNO3-KHSO4-P2O5 Containing Different Additives.

Low-temperature (350 °C) vitrification in a KNO3-NaNO3-KHSO4-NH4H2PO4 system, containing various additives to improve the chemical durability of the obtained material, was investigated. It was shown that a glass-forming system with 4.2-8.4 wt.% Al nitrate admixtures could form stable and transparent glasses, whereas the addition of H3BO3 produced a glass-matrix composite containing BPO4 crystalline inclusions. Mg nitrate admixtures inhibited the vitrification process and only allowed obtaining glass-matrix composites with combinations with Al nitrate and boric acid. Using ICP and low-energy EDS point analyses, it was recognized that all the obtained materials contained nitrate ions in their structure. Various combinations of the abovementioned additives favored liquid phase immiscibility and crystallization of BPO4, KMgH(PO3)3, with some unidentified crystalline phases in the melt. The mechanism of the vitrification processes taking place in the investigated systems, as well as the water resistance of the obtained materials, was analyzed. It was shown that the glass-matrix composites based on the (K,Na)NO3-KHSO4-P2O5 glass-forming system, containing Al and Mg nitrates and B2O3 additives, had increased water resistance, in comparison with the parent glass composition, and could be used as controlled-release fertilizers containing the main useful nutrients (K, P, N, Na, S, B, and Mg).

Structure and Properties of the Xerogels Based on Potassium Silicate Liquid Glass and Urea.

The xerogels based on the aqueous solutions of urea in potassium silicate liquid glass (PSLG) were produced by CO2 bubbling and investigated. The structure and chemical composition of the obtained materials were analyzed. Using the SEM, XRD, IR-FT, DSC, and low energy local EDS analysis, it was recognized that the dried gels (xerogels) contained three forms of urea: oval crystals of regular shape appeared onto the surface of xerogel particles; fibrous crystals were located in the silicate matrix; and molecules/ions were incorporated into the silicate matrix. It was shown that an increase in [(NH2)2CO] in the gel-forming system promoted increased contents in crystalline forms of urea as well as the diameter of the fiber-shaped urea crystals. A rate of the urea release in water from the granulated xerogels containing 5.8, 12.6, and 17.9 wt.% of urea was determined by the photometric method. It was determined that the obtained urea-containing xerogels were characterized with a slow release of urea, which continued up to 120 days, and could be used as controlled release fertilizers containing useful nutrients (N, K).

The Conditions Matter: The Toxicity of Titanium Trisulfide Nanoribbons to Bacteria E. coli Changes Dramatically Depending on the Chemical Environment and the Storage Time.

In this work, we present an analysis of the antibacterial activity of TiS3 nanostructures in water and 0.9% NaCl solution suspensions. TiS3 nanoribbons 1-10 µm long, 100-300 nm wide, and less than 100 nm thick were produced by the direct reaction of pure titanium powder with elemental sulphur in a quartz tube sealed under vacuum. For the toxicity test of a bioluminescent strain of E. coli we used concentrations from 1 to 0.0001 g L-1 and also studied fresh suspensions and suspensions left for 24 h. The strongest toxic effect was observed in freshly prepared water solutions where the luminescence of bacteria decreased by more than 75%. When saline solution was substituted for water or when the solutions were stored for 24 h it resulted in a considerable decrease in the TiS3 antibacterial effect. The toxicity of TiS3 in water exceeded the toxicity of the reference TiO2 nanoparticles, though when saline solution was used instead of water the opposite results were observed. In addition, we did not find a relationship between the antibacterial activity of water suspensions of nanoribbons and the stability of their colloidal systems, which indicates an insignificant contribution to the toxicity of aggregation processes. In 0.9% NaCl solution suspensions, toxicity increased in proportion to the increase in the zeta potential. We suppose that the noted specificity of toxicity is associated with the emission of hydrogen sulphide molecules from the surface of nanoribbons, which, depending on the concentration, can either decrease or increase oxidative stress, which is considered the key mechanism of nanomaterial cytotoxicity. However, the exact underlying mechanisms need further investigation. Thus, we have shown an important role of the dispersion medium and the period of storage in the antibacterial activity of TiS3 nanoribbons. Our results could be used in nanotoxicological studies of other two-dimensional nanomaterials, and for the development of novel antibacterial substances and other biomedical applications of this two-dimensional material.

Cyan Fluorescent Carbon Quantum Dots with Amino Derivatives for the Visual Detection of Copper (II) Cations in Sea Water.

Amino- and carboxyl-functionalized carbon quantum dots (Amino-CQDs) were synthesized through fast and simple microwave treatment of a citric acid, ethylenediamine and ethylenediaminetetraacetic acid (EDTA) mix. The reproducible and stable optical properties from newly synthesized CQD dispersion with a maximum absorbance spectra at 330 nm and the symmetric emission maximum at 470 nm made the Amino-CQDs a promising fluorescence material for analytical applications. The highly aminated and chelate moieties on the CQDs was appropriate for a copper (Cu2+) cation sensor in the linear range from 1 × 10-4 mg/mL to 10 mg/mL with a limit of detection at 0.00036 mg/mL by static fluorescence quenching effects. Furthermore, Amino-CQDs demonstrated stable fluorescence parameters for assays in diluted alkali metal solution (Na+ and K+) and sea water. Finally, a visual sensor, based on Amino-CQDs, was successfully created for the 0.01-100 mg/mL range to produce a colorimetric effect that can be registered by computer vision software (Open CV Python).

Role of Polyanions and Surfactant Head Group in the Formation of Polymer-Colloid Nanocontainers.

OBJECTIVES: This study was aimed at the investigation of the supramolecular systems based on cationic surfactants bearing cyclic head groups (imidazolium and pyrrolidinium) and polyanions (polyacrylic acid (PAA) and human serum albumin (HSA)), and factors governing their structural behavior to create functional nanosystems with controlled properties. Research hypothesis. Mixed PE-surfactant complexes based on oppositely charged species are characterized by multifactor behavior strongly affected by the nature of both components. It was expected that the transition from a single surfactant solution to an admixture with PE might provide synergetic effects on structural characteristics and functional activity. To test this assumption, the concentration thresholds of aggregation, dimensional and charge characteristics, and solubilization capacity of amphiphiles in the presence of PEs have been determined by tensiometry, fluorescence and UV-visible spectroscopy, and dynamic and electrophoretic light scattering. RESULTS: The formation of mixed surfactant-PAA aggregates with a hydrodynamic diameter of 100-180 nm has been shown. Polyanion additives led to a decrease in the critical micelle concentration of surfactants by two orders of magnitude (from 1 mM to 0.01 mM). A gradual increase in the zeta potential of HAS-surfactant systems from negative to positive value indicates that the electrostatic mechanism contributes to the binding of components. Additionally, 3D and conventional fluorescence spectroscopy showed that imidazolium surfactant had little effect on HSA conformation, and component binding occurs due to hydrogen bonding and Van der Waals interactions through the tryptophan amino acid residue of the protein. Surfactant-polyanion nanostructures improve the solubility of lipophilic medicines such as Warfarin, Amphotericin B, and Meloxicam. PERSPECTIVES: Surfactant-PE composition demonstrated beneficial solubilization activity and can be recommended for the construction of nanocontainers for hydrophobic drugs, with their efficacy tuned by the variation in surfactant head group and the nature of polyanions.

Quantum dots are time bomb: Multiscale toxicological study.

The use of quantum dots has spread widely into many applications. Works on the study of quantum dots on living organisms have had conflicting results on toxicity. There are no full-scale long-term toxicological studies with multiple administration of quantum dots. Understanding the toxicity of quantum dots is still limited. Here we present data on the effects of quantum dots on animals. In this work for the first time, it is shown that at a single administration of quantum dots in the body they have moderate species-specific toxicity, but repeated administration of quantum dots for 14 days even in the amount of 0.5 mg/kg leads to a delayed not completely irreversible hematotoxic effect, delayed irreversible disorders of barrier function of the liver, irreversible nephrotoxic effect, and to pathological changes in the thymus, kidneys and spleen. Administration of quantum dots in the amount of 2.5 mg/kg for 14 days leads to irreversible changes in the lungs, liver, spleen, kidneys and thyroid gland. This phenomenon is based on immunological reactions. On the one hand, these data confirm that quantum dots at a single administration can show relatively low toxicity. On the other hand, they cause to a delayed irreversible organ and tissue damage when repeatedly administered to the body even in small quantities. This study demonstrates that quantum dots are not as low in toxicity as previously thought to be and pose a serious risk when entering living organisms. Detecting and treating poisoning using standard methods of diagnosis and treatment of heavy metal poisoning may not be effective. This study demonstrates that toxic effects of quantum dots on a living body are quite complex and cannot be generalized based on previously reported assumptions.

Graphene Oxide Nanosurface Reduces Apoptotic Death of HCT116 Colon Carcinoma Cells Induced by Zirconium Trisulfide Nanoribbons.

Due to their chemical, mechanical, and optical properties, 2D ultrathin nanomaterials have significant potential in biomedicine. However, the cytotoxicity of such materials, including their mutual increase or decrease, is still not well understood. We studied the effects that graphene oxide (GO) nanolayers (with dimensions 0.1-3 µm and average individual flake thickness less than 1 nm) and ZrS3 nanoribbons (length more than 10 µm, width 0.4-3 µm, and thickness 50-120 nm) have on the viability, cell cycle, and cell death of HCT116 colon carcinoma cells. We found that ZrS3 exhibited strong cytotoxicity by causing apoptotic cell death, which was in contrast to GO. When adding GO to ZrS3, ZrS3 was significantly less toxic, which may be because GO inhibits the effects of cytotoxic hydrogen sulfide produced by ZrS3. Thus, using zirconium trisulfide nanoribbons as an example, we have demonstrated the ability of graphene oxide to reduce the cytotoxicity of another nanomaterial, which may be of practical importance in biomedicine, including the development of biocompatible nanocoatings for scaffolds, theranostic nanostructures, and others.

The Formation of Morphologically Stable Lipid Nanocarriers for Glioma Therapy.

Cerasomes are a promising modification of liposomes with covalent siloxane networks on the surface that provide outstanding morphological stability while maintaining all the useful traits of liposomes. Herein, thin film hydration and ethanol sol injection methods were utilized to produce cerasomes of various composition, which were then evaluated for the purpose of drug delivery. The most promising nanoparticles obtained by the thin film method were studied closely using MTT assay, flow cytometry and fluorescence microscopy on T98G glioblastoma cell line and modified with surfactants to achieve stability and the ability to bypass the blood-brain barrier. An antitumor agent, paclitaxel, was loaded into cerasomes, which increased its potency and demonstrated increased ability to induce apoptosis in T98G glioblastoma cell culture. Cerasomes loaded with fluorescent dye rhodamine B demonstrated significantly increased fluorescence in brain slices of Wistar rats compared to free rhodamine B. Thin film hydration with Tween 80 addition was established as a more reliable and versatile method for cerasome preparation. Cerasomes increased the antitumor action of paclitaxel toward T98G cancer cells by a factor of 36 and were able to deliver rhodamine B over the blood-brain barrier in rats.

Altering Oxygen Binding by Redox-Inactive Metal Substitution to Control Catalytic Activity: Oxygen Reduction on Manganese Oxide Nanoparticles as a Model System.

Establishing generic catalyst design principles by identifying structural features of materials that influence their performance will advance the rational engineering of new catalytic materials. In this study, by investigating metal-substituted manganese oxide (spinel) nanoparticles, Mn3 O4 :M (M=Sr, Ca, Mg, Zn, Cu), we rationalize the dependence of the activity of Mn3 O4 :M for the electrocatalytic oxygen reduction reaction (ORR) on the enthalpy of formation of the binary MO oxide, Δf H°(MO), and the Lewis acidity of the M2+ substituent. Incorporation of elements M with low Δf H°(MO) enhances the oxygen binding strength in Mn3 O4 :M, which affects its activity in ORR due to the established correlation between ORR activity and the binding energy of *O/*OH/*OOH species. Our work provides a perspective on the design of new compositions for oxygen electrocatalysis relying on the rational substitution/doping by redox-inactive elements.

Advancing MXene Electrocatalysts for Energy Conversion Reactions: Surface, Stoichiometry, and Stability.

MXenes, due to their tailorable chemistry and favourable physical properties, have great promise in electrocatalytic energy conversion reactions. To exploit fully their enormous potential, further advances specific to electrocatalysis revolving around their performance, stability, compositional discovery and synthesis are required. The most recent advances in these aspects are discussed in detail: surface functional and stoichiometric modifications which can improve performance, Pourbaix stability related to their electrocatalytic operating conditions, density functional theory and advances in machine learning for their discovery, and prospects in large scale synthesis and solution processing techniques to produce membrane electrode assemblies and integrated electrodes. This Review provides a perspective that is complemented by new density functional theory calculations which show how these recent advances in MXene material design are paving the way for effective electrocatalysts required for the transition to integrated renewable energy systems.

Complexation of Oligo- and Polynucleotides with Methoxyphenyl-Functionalized Imidazolium Surfactants.

Interaction between cationic surfactants and nucleic acids attracts much attention due to the possibility of using such systems for gene delivery. Herein, the lipoplexes based on cationic surfactants with imidazolium head group bearing methoxyphenyl fragment (MPI-n, n = 10, 12, 14, 16) and nucleic acids (oligonucleotide and plasmid DNA) were explored. The complex formation was confirmed by dynamic/electrophoretic light scattering, transmission electron microscopy, fluorescence spectroscopy, circular dichroism, and gel electrophoresis. The nanosized lipoplex formation (of about 100-200 nm), contributed by electrostatic, hydrophobic interactions, and intercalation mechanism, has been shown. Significant effects of the hydrocarbon tail length of surfactant and the type of nucleic acid on their interaction was revealed. The cytotoxic effect and transfection ability of lipoplexes studied were determined using M-HeLa, A549 cancer cell lines, and normal Chang liver cells. A selective reduced cytotoxic effect of the complexes on M-HeLa cancer cells was established, as well as a high ability of the systems to be transfected into cancer cells. MPI-n/DNA complexes showed a pronounced transfection activity equal to the commercial preparation Lipofectamine 3000. Thus, it has been shown that MPI-n surfactants are effective agents for nucleic acid condensation and can be considered as potential non-viral vectors for gene delivery.

Therapy of Organophosphate Poisoning via Intranasal Administration of 2-PAM-Loaded Chitosomes.

Chitosan-decorated liposomes were proposed for the first time for the intranasal delivery of acetylcholinesterase (AChE) reactivator pralidoxime chloride (2-PAM) to the brain as a therapy for organophosphorus compounds (OPs) poisoning. Firstly, the chitosome composition based on phospholipids, cholesterol, chitosans (Cs) of different molecular weights, and its arginine derivative was developed and optimized. The use of the polymer modification led to an increase in the encapsulation efficiency toward rhodamine B (RhB; ~85%) and 2-PAM (~60%) by 20% compared to conventional liposomes. The formation of monodispersed and stable nanosized particles with a hydrodynamic diameter of up to 130 nm was shown using dynamic light scattering. The addition of the polymers recharged the liposome surface (from -15 mV to +20 mV), which demonstrates the successful deposition of Cs on the vesicles. In vitro spectrophotometric analysis showed a slow release of substrates (RhB and 2-PAM) from the nanocontainers, while the concentration and Cs type did not significantly affect the chitosome permeability. Flow cytometry and fluorescence microscopy qualitatively and quantitatively demonstrated the penetration of the developed chitosomes into normal Chang liver and M-HeLa cervical cancer cells. At the final stage, the ability of the formulated 2-PAM to reactivate brain AChE was assessed in a model of paraoxon-induced poisoning in an in vivo test. Intranasal administration of 2-PAM-containing chitosomes allows it to reach the degree of enzyme reactivation up to 35 ± 4%.

Use of folic acid nanosensors with excellent photostability for hybrid imaging.

Sentinel lymph node (SLN) mapping and tumor-boundary delineation play a key role in cancer surgery, as they have great potential to reduce surgical intervention and increase relapse-free survival rates of patients. The autofluorescence imaging (AFI) method can improve the efficiency of tumor delineation and optimize the scope of surgical intervention, but there are still no fluorescent drugs that can be used with such a method to form a hybrid imaging technique. Another problem is bleaching when fluorescent dyes are conjugated with folic acid. This study reports, for the first time, nanosensors with excellent photostability and compatibility with endoscopes for AFI, which makes simultaneous hybrid imaging possible. After functionalization of the quantum dot (QD) surfaces, we found that they bound effectively to MCF-7 cancer cells. The diagnostic value of simultaneous hybrid imaging using common AFI equipment in delineating tumor boundaries and mapping SLN can reduce the cost of diagnosis and increase its reliability.

Oxime Therapy for Brain AChE Reactivation and Neuroprotection after Organophosphate Poisoning.

One of the main problems in the treatment of poisoning with organophosphorus (OPs) inhibitors of acetylcholinesterase (AChE) is low ability of existing reactivators of AChE that are used as antidotes to cross the blood-brain barrier (BBB). In this work, modified cationic liposomes were developed that can penetrate through the BBB and deliver the reactivator of AChE pralidoxime chloride (2-PAM) into the brain. Liposomes were obtained on the basis of phosphatidylcholine and imidazolium surfactants. To obtain the composition optimized in terms of charge, stability, and toxicity, the molar ratio of surfactant/lipid was varied. For the systems, physicochemical parameters, release profiles of the substrates (rhodamine B, 2-PAM), hemolytic activity and ability to cause hemagglutination were evaluated. Screening of liposome penetration through the BBB, analysis of 2-PAM pharmacokinetics, and in vivo AChE reactivation showed that modified liposomes readily pass into the brain and reactivate brain AChE in rats poisoned with paraoxon (POX) by 25%. For the first time, an assessment was made of the ability of imidazolium liposomes loaded with 2-PAM to reduce the death of neurons in the brains of mice. It was shown that intravenous administration of liposomal 2-PAM can significantly reduce POX-induced neuronal death in the hippocampus.

Enhancement of the Transdermal Delivery of Nonsteroidal Anti-inflammatory Drugs Using Liposomes Containing Cationic Surfactants.

New hybrid liposomes based on cationic amphiphiles with different structures of the head group (cetyltrimethylammonium bromide (CTAB), 3-hexadecyl-1-hydroxyethylimidazolium bromide (IA-16(OH)), 1-(butylcarbamoyl)oxyethyl-3-hexadecylimidazolium bromide (IAC 16(Bu)), and hexadecylmethylpyrrolidinium bromide (PR-16)) were developed for transdermal administration of nonsteroidal anti-inflammatory drugs. The different surfactant/lipid compositions were studied to obtain stable liposomes with high functionality. The hydrodynamic diameter of cationic liposomes was ∼110 nm. An admixture of cationic surfactants and PC liposomes improves the physicochemical properties of vesicles and transdermal diffusion rate and prolongs the release of drugs. Liposomal diclofenac sodium (DS) and ketoprofen (KP) were tested (using Franz cells) for transdermal penetration. Drug diffusion monitoring for 48 h demonstrated that the maximum DS and KP penetration through the synthetic membranes (Strat-M) is characterized by values of 255 ± 2 and 186 ± 3 µg/cm2, respectively. The influence of the surfactant head group on the properties (stability, release profile, permeability) of cationic liposomes was shown for the first time. While the drug specificity is evident for the rate of release, the permeability increases as follows: conventional liposomes < CTAB/PC < PR-16/PC < IAC-16(Bu)/PC < IA-16(OH)/PC for both medicines. The rat paw edema model was used to assess the anti-inflammatory effect of the IA-16(OH)/PC leader formulation in vivo. It was found that liposomal DS and KP are effective for relieving rat paw edema. It should be noted that DS-loaded hybrid liposomes demonstrated the highest therapeutic efficacy compared to conventional vesicles.