Molecularly imprinted polymer (MIP) and magnetic molecularly imprinted polymer (mag-MIP) for solid extraction and pre-concentration of quercetin have been successfully prepared by thermal ...polymerization method using quercetin (Q) as a template, acrylamide (AA) as a functional monomer, and ethylene glycol dimethacrylate (EGDMA) as a cross-linking agent. The MIP and mag-MIP were successfully applied in analysis of quercetin by mass spectrometry (MS) methods. To perform ambient plasma ionization experiments, a setup consisting of the heated crucible, a flowing atmospheric-pressure afterglow (FAPA) plasma ion source, and amaZon SL ion trap (Bruker, Bremen, Germany) was used. The heated crucible with programmable temperature allowed desorption of the analytes from MIPs structure which resulted in their direct introduction into the ion stream. The results of Q-MIP/Q-mag-MIP and FAPA-MS measurements were compared with those of the analysis of quercetin by the ESI-MS method without extractions and pre-concentration of analytes on polymers. Limits of detection (LOD) for quercetin solutions in both positive and negative ESI-MS were established at 10
M and 10
M, respectively. The linearity (R
= 0.9999) of the proposed analytical procedure for quercetin determination in positive ions was provided in the range between 10
M and 10
M. Moreover, the same parameters were established for FAPA-MS in positive ions, reaching LOD at 0.005 mg/gMIP and the linearity of the method in the range of 0.015-0.075 mg/gMIP with the correlation coefficient value R
= 0.9850.
The following research aims at the synthesis of magnetite nanoparticles functionalized with triazine-based dendrons and the application of the obtained materials as effective sorptive materials ...dedicated to acidic bioactive compounds. The adopted synthetic approach involved: (1) the synthesis of nanosized Fe
O
particles via classic co-precipitation method, (2) the introduction of amine groups on their surface leading to materials' precursor, and (3) the final synthesis of branched triazine-based dendrons on the support surface by an iterative reaction between cyanuric chloride (CC) and piperazine (p) or diethylenetriamine (DETA) via nucleophilic substitution. The characterized materials were tested for their adsorptive properties towards folic acid, 18β-glycyrrhetinic acid, and vancomycin, showing high adsorption capacities varying in the ranges of 53.33-401.61, 75.82-223.71, and 68.17-132.45 mg g
, respectively. The formed material-drug complexes were also characterized for the drug-delivery potential, performed as in vitro release studies at pH 2.0 and 7.4, which mimics the physiological conditions. The release profiles showed that the proposed materials are able to deliver up to 95.2% of the drugs within 48 h, which makes them efficient candidates for further biomedical applications.
One of the major goals in the materials science is the design and development of non-toxic, versatile, and efficient drug delivery systems. The study reported in this paper concerns the syntheses of ...poly(amidoamine) (PAMAM) dendrimers with tris(2-aminoethyl)amine as an amine core and different terminal amines, and their attachment to silica matrix. The obtained ethylenediamine (EDA), triethylenetetramine (TETA), tris(2-aminoethyl)amine (TREN) and 4,7,10-trioxa-1,13-tridecanediamine (TRI-OXA) dendrimers were introduced to the support surface via an epoxy linker, leading to a loading efficiency in the range of 0.054-0.113 mmol g
, determined using elemental and thermogravimetric analyses. The materials exhibited high adsorption capacities towards the chosen model drugs: folic, salicylic and nicotinic acid. The investigated adsorption processes were found to follow the Freundlich isotherm model, with indication of the drugs' structure influence on the binding efficiency. Drug-loaded hybrid materials were also described for in vitro drug release in three pH-different paraphysiological media. The highest percentage release was obtained in the tests performed at pH 2.0, ranging between 35.42 and 99.83%. Satisfactory results and the versatility of PAMAM dendrimers may lead to the application of such materials not only as drug carriers dedicated to a wide range of pharmaceutics, but also as analytical tools for pre-concentration and/or the determination of biocompound contamination in samples.
Qualitative and quantitative analysis of estrogens content in natural water is a difficult task. An important problem in the analysis of hormones in water is the quantitative determination of their ...individual species. Low detection limits and instability of estrogen derivatives are the main challenges. Magnetic molecularly imprinted polymers (mag-MIPs) in combination with Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (FAPA-MS) were successfully used for analysis of estrogen hormones in water samples. The aim of the study was to obtain mag-MIPs selective to estrone (E1) and β-estradiol (E2) for solid phase extraction and pre-concentration of estrogens. Due to their superior analyte binding properties at low concentrations (0.03 g in 1 g of polymer structure) and possibility of magnetic separation, mag-MIPs were proven to be very convenient and efficient adsorbent materials. In addition, MS analyses were performed using two ionization sources: ESI- and FAPA-MS. For both estrogens, LOD was significantly lower for FAPA-MS analysis (0.135 μgL
for E1 and E2) than for ESI-MS analysis (27 μgL
for E1 and 13.6 μgL
for E2). The total estrogen concentration in the environmental water sample was determined as: cE1 = 0.271 μgL
and cE2 = 0.275 μgL
.
Deferoxamine (DFO) is one of the most potent iron ion complexing agent belonging to a class of trihydroxamic acids. The extremely high stability constant of the DFO–Fe complex (log β = 30.6) prompts ...the use of deferoxamine as a targeted receptor for scavenging Fe(III) ions. The following study aimed at deferoxamine immobilization on three different supports: poly(methyl vinyl ether-alt-maleic anhydride), silica particles, and magnetite nanoparticles, leading to a class of hybrid materials exhibiting effectiveness in ferric ion adsorption. The formed deferoxamine-loaded hybrid materials were characterized with several analytical techniques. Their adsorptive properties toward Fe(III) ions in aqueous samples, including pH-dependence, isothermal, kinetic, and thermodynamic experiments, were investigated. The materials were described with high values of maximal adsorption capacity q m, which varied between 87.41 and 140.65 mg g–1, indicating the high adsorptive potential of the DFO-functionalized materials. The adsorption processes were also described as intense, endothermic, and spontaneous. Moreover, an exemplary magnetically active deferoxamine-modified material has been proven for competitive in vitro binding of ferric ions from the biological complex protoporphyrin IX–Fe(III), which may lead to a further examination of the materials’ biological or medical applicability.
The influence of an inorganic support – halloysite nanotubes – on the release rate and biological activity of the antibiotic encapsulated in alginate-based dressings was studied. The halloysite ...samples were loaded with approx. 10wt.% of the antibiotic and then encapsulated in Alginate and Gelatin/Alginate gels. The material functionalized with aliphatic amine significantly extended the release of vancomycin from alginate-based gels as compared to that achieved when silica was used. After 24h, the released amounts of the antibiotic immobilized at silica reached 70%, while for the drug immobilized at halloysite the released amount of vancomycin reached 44% for Alginate discs. The addition of gelatin resulted in even more prolonged sustained release of the drug. The antibiotic was released from the system with a double barrier with Higuchi kinetic model and Fickian diffusion mechanism. Only the immobilized drug encapsulated in Alginate gel demonstrated very good antimicrobial activity against various bacteria. The inhibition zones were greater than those of the standard discs for the staphylococci and enterococci bacteria tested. The addition of gelatin adversely affected the biological activity of the system. The inhibition zones were smaller than those of the reference samples. A reduction in the drug dose by half had no significant effect on changing the release rate and microbiological activity. The in vivo toxicity studies of the material with immobilized drug were carried out with Acutodesmus acuminatus and Daphnia magna. The material studied had no effect on the living organisms used in the bioassays. The proposed system with a double barrier demonstrated high storage stability.
This article shows that nanodiamonds can transmigrate through the insect cuticle easily, and the doses used were not hemocytotoxic and did not cause inhibition of cellular and humoral immune ...responses in larvae, pupae and adults of Tenebrio molitor. The examination of the nanodiamond biodistribution in insect cells demonstrated the presence of nanodiamond aggregates mainly in hemocytes, where nanoparticles were efficiently collected as a result of phagocytosis. To a lesser extent, nanodiamond aggregates were also detected in fat body cells, while they were not observed in Malpighian tubule cells. We functionalized nanodiamonds with Neb-colloostatin, an insect hemocytotoxic and gonadoinhibitory peptide, and we showed that this conjugate passed through the insect cuticle into the hemolymph, where the peptide complexed with the nanodiamonds induced apoptosis of hemocytes, significantly decreased the number of hemocytes circulating in the hemolymph and inhibited cellular and humoral immune responses in all developmental stages of insects. The results indicate that it is possible to introduce a peptide that interferes with the immunity and reproduction of insects to the interior of the insect body by means of a nanocarrier. In the future, the results of these studies may contribute to the development of new pest control agents.
In recent years, the rapid development of the pharmaceutical industry and the extensive and illicit use of painkillers have led to increased levels of nonsteroidal anti-inflammatory drugs (NSAIDs) in ...the environment. In view of the significant impact of NSAIDs on living organisms, including humans, their presence in the environment needs to be continuously monitored at trace levels. For this purpose, a combination of molecularly imprinted solid-phase extraction (MISPE) and HPLC-MS analysis is commonly used. MISPE has been utilized in direct, fast, and ecological analysis of drugs using a flowing atmospheric-pressure afterglow ion source for mass spectrometry (FAPA-MS). The new method was applied herein in the determination of naproxen, diclofenac, and ibuprofen. The linear dependence of the intensity of analytical signals on the amount of drugs is in the range of 0.2 μg to 1 g and the method detection limit (MDL) for all drugs is 0.2 μg in environmental samples. The new method also decreased the number of analytical stages, the time and cost of analysis, and the organic solvent consumption, besides being environmentally friendly.
This work continues our studies on the pleiotropic activity of the insect peptide Neb-colloostatin in insects. In vivo immunological bioassays demonstrated that hemocytotoxic analogs of ...Neb-colloostatin injected into Tenebrio molitor significantly reduced the number of hemocytes in the hemolymph and impaired phagocytosis, nodulation and phenoloxidase activities in the insects. Among the analogs tested, Ala
-,Val
-, Hyp
- and Ach
-colloostatin were particularly potent in disrupting cellular immunity in larvae, pupae and adult insects. This result suggests that the most effective analogs showed increases in the bioactivity period in the hemolymph of insects when compared to Neb-colloostatin. Recently, we demonstrated that it is possible to introduce Neb-colloostatin through the cuticle of an insect into the hemolymph when the peptide is coupled with nanodiamonds. In this study, we showed that Ala
-, Val
-, Hyp
- and Ach
-colloostatin, when complexed with nanodiamonds, may also pass through the cuticle into the hemolymph and induce long-term impairments of immunity in T. molitor at all developmental stages. Studies on the tissue selectivity and effectiveness of Neb-colloostatin analogs and efficient methods for their introduction into insects may contribute to the development of eco-friendly pest control methods based on bioactive peptidomimetics.
Chalcones are naturally occurring compounds exhibiting multiple biological functions related to their structure. The investigation of complexes formed by chalcones, namely ...2',4'-dihydroxy-2-methoxychalcone (DH-2-MC) and 2',4'-dihydroxy-3-methoxychalcone (DH-3-MC), with organo-functionalized Fe
O
magnetic nanoparticles using mass spectrometric techniques is reported. The magnetic nanoparticles were obtained by the silanization of Fe
O
particles with 3-aminopropyltrimethosysilane, which were subsequently reacted with 3-hydroxybenzaldehyde (3-HBA) or 2-pyridinecarboxaldehyde (2-PCA), resulting in the formation of Schiff base derivatives. The formation of their complexes with chalcones was studied using electrospray (ESI) and flowing atmosphere-pressure afterglow (FAPA) mass spectrometric (MS) ionization techniques. The functional nanoparticles which were synthesized using 3-hydroxybenzaldehyde displayed higher affinity towards examined chalcones than their counterparts obtained using 2-pyridinecarboxaldehyde, which has been proved by both ESI and FAPA techniques. For the examined chalcones, two calibration curves were obtained using the ESI-MS method, which allowed for the quantitative analysis of the performed adsorption processes. The presence of Cu(II) ions in the system significantly hindered the formation of material-chalcone complexes, which was proved by the ESI and FAPA techniques. These results indicate that both mass spectrometric techniques used in our study possess a large potential for the investigation of the binding properties of various functional nanoparticles.
PDF
