Charged Amino Research Articles

Atomistic insights into the K+/Na+ separation across amino modified graphene nanopore: The assisting role of Cl−

K+/Na+ separation has always been considered the most challenging. We adopted molecular dynamics to compare graphene nanopores modified with positively charged amino groups and their pristine counterparts to unravel the mechanism underlying the effect of positively charged amino groups on K+/Na+ separation and evaluate the assisting effect of Cl−. Two pore diameters of approximately 1 nm were selected. Results demonstrated that nanopore modification can effectively improve the K+/Na+ selectivity, and the spatial distribution and residence time of Cl− near the nanopores indicated that modification with positively charged amino groups can induce the dynamical adsorption of Cl− around the nanopores. In the studied nanopores, the prolongation of the residence time of Cl− at the pore mouths can increase the difference between K+ and Na+ dehydration and thus can increase their transport resistance difference. The latter effect is conducive to improving the selectivity for K+. Our findings can provide useful insight for the further design of K+ separating two-dimensional materials as sensors and ion separators.

Short Lysine-Containing Tripeptide as Analgesic Substance: The Possible Mechanism of Ligand–Receptor Binding to the Slow Sodium Channel

A possible molecular mechanism of the ligand–receptor binding of Ac-Lys-Lys-Lys-NH2 (Ac-KKK-NH2) to the NaV1.8 channel that is responsible for nociceptive signal coding in the peripheral nervous system is investigated by a number of experimental and theoretical techniques. Upon Ac-KKK-NH2 application at 100 nM, a significant decrease in the effective charge carried by the NaV1.8 channel activation gating system Zeff is demonstrated in the patch-clamp experiments. A strong Ac-KKK-NH2 analgesic effect at both the spinal and supraspinal levels is detected in vivo in the formalin test. The distances between the positively charged amino groups in the Ac-KKK-NH2 molecule upon binding to the NaV1.8 channel are 11–12 Å, as revealed by the conformational analysis. The blind docking with the NaV1.8 channel has made it possible to locate the Ac-KKK-NH2 binding site on the extracellular side of the voltage-sensing domain VSDI. The Ac-KKK-NH2 amino groups are shown to form ionic bonds with Asp151 and Glu157 and a hydrogen bond with Thr161, which affects the coordinated movement of the voltage sensor up and down, thus modulating the Zeff value. According to the results presented, Ac-KKK-NH2 is a promising candidate for the role of an analgesic medicinal substance that can be applied for pain relief in humans.

Ultramicroporous zinc-aminotriazole MOF with customized alkaline pore environments for highly efficient capture of CO2 from flue gas

CO2 capture from natural gas and N2-rich flue gas is essential for improving the utilization of natural resource gases reducing CO2 emission, thereby alleviating the greenhouse effect. However, achieving effective Adsorptive separation of CO2 from CH4, N2, and O2 based on molecular sieving is still challenging and rarely reported, but selectively capturing CO2 places high desires on maximizing separation efficiency. Here, we report a zinc-aminotriazole ultramicroporous metal–organic framework (ZnATZoxH2O), constructed from zinc carbonate, 3-amino-1,2,4-triazole (ATZ), and oxalic acid with water as the only solvent. ZnATZoxH2O features NH2-functionalized and pore channels around 3.6 Å, which preferentially adsorb CO2. This material exhibits high CO2 uptake of 61.9 cm3 g−1 at 298 K and 1 bar and significantly high IAST selectivity for CO2/N2 (>103) and CO2/CH4 (>105) and CO2/O2 (>104). Theoretical GCMC simulations reveal that negatively charged amino groups decorated on the pore channel surface and carboxylic acid in the pore environment enhance the binding affinity over CO2 through electrostatic interactions for preferential capture of CO2. Single-component adsorption experiments and dynamic breakthrough experiments mutually validated the superior separation performance of this material and dynamic column breakthrough tests to produce high dynamic CO2 separation productivity of 2.017 mmol g−1 and 3.4 mmol g−1 for CO2/N2 (15/85), CO2/CH4 (50/50), and 2.26mmol g−1 CO2/N2/O2 (15/80/5). Non-hazardous water as a synthetic solvent to assemble highly stable and efficient CO2-selective materials makes it promising for practical industrial applications.

Gene Therapy with Chitosan Nanoparticles: Modern Formulation Strategies for Enhancing Cancer Cell Transfection.

Gene therapy involves the introduction of exogenous genetic material into host tissues to modify gene expression or cellular properties for therapeutic purposes. Initially developed to address genetic disorders, gene therapy has expanded to encompass a wide range of conditions, notably cancer. Effective delivery of nucleic acids into target cells relies on carriers, with non-viral systems gaining prominence due to their enhanced safety profile compared to viral vectors. Chitosan, a biopolymer, is frequently utilized to fabricate nanoparticles for various biomedical applications, particularly nucleic acid delivery, with recent emphasis on targeting cancer cells. Chitosan's positively charged amino groups enable the formation of stable nanocomplexes with nucleic acids and facilitate interaction with cell membranes, thereby promoting cellular uptake. Despite these advantages, chitosan-based nanoparticles face challenges such as poor solubility at physiological pH, non-specificity for cancer cells, and inefficient endosomal escape, limiting their transfection efficiency. To address these limitations, researchers have focused on enhancing the functionality of chitosan nanoparticles. Strategies include improving stability, enhancing targeting specificity, increasing cellular uptake efficiency, and promoting endosomal escape. This review critically evaluates recent formulation approaches within these categories, aiming to provide insights into advancing chitosan-based gene delivery systems for improved efficacy, particularly in cancer therapy.

Highly sensitive and selective detection of dopamine using atomic layer deposited HfO2 ultra-thin films

The development of non-enzymatic and binder-free biosensors plays a vital role, and it possesses main benefits for effective biomolecule recognition with high sensitivity and preferred selectivity. Herein, an atomic layer deposition (ALD) was employed to develop the hafnium oxide (HfO2) nanofilm on silicon (Si) for fabricating binder-free selective and sensitive determination of the non-enzymatic electrochemical dopamine sensor. The prepared HfO2 nanofilm selectively acted as a local dopamine binding site because of the hydrophobic-hydrophobic interaction between fabricated film and dopamine, electrostatic attraction between negatively charged hydroxyl group on film surfaces, and positively charged amino group of dopamine. The developed insufficient oxygen vacancies on the HfO2 could have behaved as a charge-trapping site for better sensing properties. The developed sensor demonstrated excellent realization in sensing dopamine with a very low detection limit (0.4 pM) and swift response time of 3s which is quite precise compared with various reported literature. The fabricated HfO2/Si electrode sensor has exhibited high sensitivity, stability, and repeatability. The selectivity of dopamine sensors was at least three orders greater than other interfering biomolecules. This work proposes the essential track for the practical realization of dopamine detection in human serum and biomedical applications.

TPU/PEI nanofibers for the efficient removal of PFOA and its analogs: Effect of pH, humic acid and co-existing ions, mechanism, and regenerative effects

Perfluorooctanoic acid (PFOA) and its analogs, such as perfluorocaproic acid (PFHxA), perfluorobutyric acid (PFBA), and perfluoro(2-methyl-3-oxahexanoic) acid (GenX), present environmental contamination concerns due to their toxicity. To addressing this, in this study, we have explored the utility of thermoplastic polyurethane/polyethyleneimine (TPU/PEI) nanofibers, synthesized via electrospinning, for the efficient removal of PFOA and its analogs from aqueous solutions. Combining the positively charged amino groups of PEI and hydrophobicity of TPU potentially enhances adsorption. Further, the TPU/PEI nanofibers exhibit a distinctive nano-phase separation morphology, creating abundant adsorption sites conducive to PFAS binding. Batch adsorption experiments indicated that TPU/PEI nanofibers possess notable adsorption capacities for PFOA and its analogs. The observed adsorption capacities were ranked as follows: PFOA (0.931 mmol/g) > PFHxA (0.872 mmol/g) > PFBA (0.827 mmol/g) > GenX (0.771 mmol/g), thus showing a correlation with their respective octanol–water partition coefficient (Kow) values. Both inorganic ions and organic matter exerted more pronounced adverse effects on the adsorption of PFBA and GenX than on those of PFOA and PFHxA. This observation can be linked to competitive adsorption with PFAS. Impressively, the TPU/PEI nanofibers maintained a high removal efficiency across multiple regeneration cycles, with more than 95 % adsorption capacity retained after five cycles. To the best of our knowledge, this study is the inaugural demonstration of utilizing a TPU and PEI blend for remediation of both long-chain and short-chain PFAS in highly polluted wastewater, positioning it as a promising, accessible material for such applications.

Chitosan-Based Nanocarriers for Pulmonary and Intranasal Drug Delivery Systems: A Comprehensive Overview of their Applications.

The optimization of respiratory health is important, and one avenue for achieving this is through the application of both Pulmonary Drug Delivery System (PDDS) and Intranasal Delivery (IND). PDDS offers immediate delivery of medication to the respiratory system, providing advantages, such as sustained regional drug concentration, tunable drug release, extended duration of action, and enhanced patient compliance. IND, renowned for its non-invasive nature and swift onset of action, presents a promising path for advancement. Modern PDDS and IND utilize various polymers, among which chitosan (CS) stands out. CS is a biocompatible and biodegradable polysaccharide with unique physicochemical properties, making it well-suited for medical and pharmaceutical applications. The multiple positively charged amino groups present in CS facilitate its interaction with negatively charged mucous membranes, allowing CS to adsorb easily onto the mucosal surface. In addition, CS-based nanocarriers have been an important topic of research. Polymeric Nanoparticles (NPs), liposomes, dendrimers, microspheres, nanoemulsions, Solid Lipid Nanoparticles (SLNs), carbon nanotubes, and modified effective targeting systems compete as important ways of increasing pulmonary drug delivery with chitosan. This review covers the latest findings on CS-based nanocarriers and their applications.

Sabatier effect based adsorption-desorption coordination via cationized chitosan for enhancing ion kinetics in zinc anodes

Interface engineering through a Sabatier effect-based adsorption–desorption coordination via cationized chitosan offers a promising approach to counteract dendritic growth, hydrogen evolution, and sluggish Zn2+ kinetics. The adsorption effect in zinc ion batteries is important for maintaining a balanced distribution of zinc ions and reducing dendrite formation. However, an excessive emphasis on the adsorption effect often neglects the desorption process of zinc ions, leading to a decrease in overall ion reaction kinetics. Herein, an adsorption–desorption synergic coating called CGP@Zn was systematically designed on zinc anodes to serve as both a Zn2+ adsorption and desorption regulator and a functional protective interface. The CGP@Zn coating exhibited zincophilic and negatively charged amino and hydroxy functional groups, which facilitated the transport of Zn2+ ions and repelled free SO42- anions. Moreover, the positively charged N+ component of the CGP@Zn coating exhibited a strong desorption effect, guaranteeing the voluble retransfer of Zn2+ and promoting intensive kinetics. Collaborating with the functional interface layer, the CGP@Zn anode demonstrated a significantly high ionic transfer number of 0.72. Furthermore, CGP@Zn symmetrical cells showed an impressive ultralong lifespan of over 5000 h with an extremely low polarization voltage of ≈80 mV at 1 mA cm−2 and 2 mAh cm−2. More encouragingly, the MnO2-based full batteries endowed with the CGP interface layer achieved a capacity of 206 mAh g -1 with a retention of 91.8 % over 500 cycles at 1C. This study offers a new perspective for designing high-performance aqueous batteries via coordination of adsorption–desorption.

Charge Density-Regulated Microchannel-Based Electrochemiluminescence Sensor for Hydrogen Sulfide Detection with a Highly Efficient Accumulation Strategy.

The electrochemiluminescence (ECL) intensity can be regulated by ionic current passing through the microchannel, which broadened the regulation of the ECL sensors. But in the early reported sensors, the electrostatic repulsion and steric hindrance caused few targets to approach the interface of the microchannel driven by concentration difference, which reduced the detection efficiency and prolonged the detection period. In this study, different accumulation strategies, such as a positive electric field and different polarity electric fields, were designed to accumulate targets in the microchannel. The interaction of azide groups and hydrogen sulfide served as a research model. Hydrogen sulfide can react with the negatively charged azide groups in the microchannel surface to produce positively charged amino groups, decreasing the negative charge density of the microchannel and thus altering the ionic current and ECL intensity. The accumulation of hydrogen sulfide at the microchannel tip can increase the collision probability with azide groups to improve the detection efficiency, and the integration of accumulation and reaction can shorten the detection period to 28 min. The hydrogen sulfide concentration on the microchannel tip accumulated by applying different polarity electric fields was 22.3-fold higher than that accumulated by applying a positive electric field. The selected research model broadened the application range of a microchannel-based ECL sensor and confirmed the universality of the microchannel-based ECL sensor.

Postbiotic characterization of a potential probiotic yeast isolate, and its microencapsulation in alginate beads coated layer-by-layer with chitosan

Considering biosafety concerns and survivability limitations of probiotics (PRO) under different stresses, application of postbiotics and encapsulated PRO has received considerable attentions. Accordingly, the objective of the present study was to investigate the postbiotic capabilities of a potential PRO yeast isolate and the effect of encapsulation with alginate (Alg) and chitosan (Ch) on its survival under SGI conditions. Sequencing results of the PCR products led to the identification of Saccharomyces cerevisiae as the selected potential PRO yeast isolated from wheat germ sourdough. High survival of the isolate under simulated gastrointestinal (SGI) conditions (95.74%), its proper adhesion abilities, as well as its potent inhibitory activity against Listeria monocytogenes (75.84%) and Aspergillus niger (77.35%) were approved. Interestingly, the yeast cell-free supernatant (CFS) showed the highest antioxidant (84.35%) and phytate-degrading (56.19%) activities compared to the viable and heat-dead cells of the isolate. According to the results of the HPLC-based assay, anti-ochratoxin A (OTA) capability of the dead cells was also significantly (P < 0.05) higher than that of the viable cell. Meanwhile, the yeast CFS had no anti-OTA and antimicrobial activities against the foodborne bacteria and fungi tested. Further, microencapsulation of the yeast isolate in Alg beads coated layer-by-layer with Ch (with 77.02% encapsulation efficacy and diameter of 1059 μm based on the field emission scanning electron microscopy analysis) significantly enhanced its survivability under SGI conditions in comparison with the free cells. In addition, electrostatic cross-linking between negatively charged carboxylic groups of Alg and positively charged amino groups of Ch was verified in accordance with Fourier transform infrared and zeta potential data. Human and/or industrial food trials in future are needed for practical applications of these emerging ingredients.

Electrostatic-Interaction-Aided Microneedle Patch for Enhanced Glucose-Responsive Insulin Delivery and Three-Meal-Per-Day Blood-Glucose Regulation.

The phenylborate-ester-cross-linked hydrogel microneedle patch (MNP) was promising in the diabetic field for the glucose-responsive insulin-delivering property and simple fabrication process. However, the unfit design of the charging microneedle network limited the improvement of blood-glucose regulating performances. In this work, insulin-loaded phenylborate-ester-cross-linked MNPs, with the polyzwitterion property, were constructed based on the modified ε-polylysine and poly(vinyl alcohol). The relationship between the charging nature of the MNP network and insulin release was verified by regulating the content of postprotonated positively charged amino groups. The elaborately designed MNP possessed improved glucose-responsive insulin-delivering performance. The in vivo study revealed the satisfactory results on blood-glucose regulation by the optimized MNP under the mimic three-meal-per-day mode. Moreover, the insulin bioactivity in the MNP could be maintained for 2 weeks under 25 °C. In summary, this work developed an effective strategy to improve the glucose-responsive phenylborate-ester-cross-linked MNP and enhance its potential for clinical transformation.

Structural, Biochemical, and Computational Characterization of Sulfamides as Bimetallic Peptidase Inhibitors.

The sulfonamide function is used extensively as a general building block in various inhibitory scaffolds and, more specifically, as a zinc-binding group (ZBG) of metalloenzyme inhibitors. Here, we provide biochemical, structural, and computational characterization of a metallopeptidase in complex with inhibitors, where the mono- and bisubstituted sulfamide functions are designed to directly engage zinc ions of a bimetallic enzyme site. Structural data showed that while monosubstituted sulfamides coordinate active-site zinc ions via the free negatively charged amino group in a canonical manner, their bisubstituted counterparts adopt an atypical binding pattern divergent from expected positioning of corresponding tetrahedral reaction intermediates. Accompanying quantum mechanics calculations revealed that electroneutrality of the sulfamide function is a major factor contributing to the markedly lower potency of bisubstituted compounds by considerably lowering their interaction energy with the enzyme. Overall, while bisubstituted uncharged sulfamide functions can bolster favorable pharmacological properties of a given inhibitor, their use as ZBGs in metalloenzyme inhibitors might be less advantageous due to their suboptimal metal-ligand properties.

Polyamines (PAs) but not small peptides with closely spaced positively charged groups interact with DNA and RNA, but they do not represent a relevant buffer system at physiological pH values.

Polyamines (PAs) including putrescine (PUT), spermidine (SPD) and spermine (SPM) are small, versatile molecules with two or more positively charged amino groups. Despite their importance for almost all forms of life, their specific roles in molecular and cellular biology remain partly unknown. The molecular structures of PAs suggest two presumable biological functions: (i) as potential buffer systems and (ii) as interactants with poly-negatively charged molecules like nucleic acids. The present report focuses on the question, whether the molecular structures of PAs are essential for such functions, or whether other simple molecules like small peptides with closely spaced positively charged side chains might be suitable as well. Consequently, we created titration curves for PUT, SPD, and SPM, as well as for oligolysines like tri-, tetra-, and penta-lysine. None of the molecules provided substantial buffering capacity at physiological intracellular pH values. Apparently, the most important mechanism for intracellular pH homeostasis in neurons is not a buffer system but is provided by the actions of the sodium-hydrogen and the bicarbonate-chloride antiporters. In a similar approach we investigated the interaction with DNA by following the extinction at 260 nm when titrating DNA with the above molecules. Again, PUT and tri-lysine were not able to interact with herring sperm DNA, while SPD and SPM were. Obviously, the presence of several positively charged groups on its own is not sufficient for the interaction with nucleic acids. Instead, the precise spacing of these groups is necessary for biological activity.

Aramid nanofiber membrane decorated with monodispersed silver nanoparticles as robust and flexible SERS chips for trace detection of multiple toxic substances

Aramid nanofibers (ANFs) as an innovative nanoscale building block exhibit great potential for novel high-performance multifunctional membranes attributed to their extraordinary performance. However, the application of aramid nanofibers in the field of surface enhanced Raman scattering (SERS) sensing has been rarely reported. In this work, aramid nanofibers derived from commercial Kevlar fibers were synthesized by a facile dimethyl sulfoxide/potassium hydroxide (DMSO/KOH) solution treatment. The monodispersed silver nanoparticle-decorated aramid nanofiber (m-Ag@ANF) membranes were constructed by an efficient vacuum filtration technique. Taking advantages of unique intrinsic properties of ANF, the m-Ag@ANF substrates exhibit good flexibility, excellent mechanical properties and prominent thermal stability. Besides, due to the abundance of positively charged amino-group on the ANF substrates, the negatively charged m-AgNPs were uniformly and firmly deposited on the surface of ANF substrate through electrostatic interactions. As a result, the optimal flexible m-Ag-9@ANF SERS substrate exhibits high sensitivity of 10-9 M for methylene blue (MB) and excellent signal reproducibility (RSD = 6.37 %), as well as outstanding signal stability (up to 15 days). Besides, the 2D Raman mapping and FDTD simulations further reveal prominent signal homogeneity and strong electric field distribution for flexible m-Ag-9@ANF SERS substrate. Finally, it is demonstrated that the flexible m-Ag-9@ANF SERS substrate can also be used for detection of toxic molecules on irregular surfaces by a feasible paste-and-read process. The m-Ag@ANF paper exhibits potential applications as a flexible, low-cost, robust and stable SERS sensing platform for trace detection of toxic materials.

Cadmium immobilization during nitrate-reducing Fe(II) oxidation by Acidovorax sp. BoFeN1: Contribution of bacterial cells and secondary minerals

Microbially nitrate-reducing Fe(II) oxidation (NRFO) is widespread in anoxic environments at circumneutral pH, in which Fe(II) oxidation is considered to be mainly catalyzed by nitrite via chemodenitrification after microbial nitrate reduction. Cadmium (Cd) is toxic to organisms, and its availability is strongly affected by iron (oxyhydr)oxides and/or bacteria. However, it remains unclear how NRFO affects the fate of Cd with environmentally relevant concentrations, and the relative contributions of microbes and secondary minerals to Cd immobilization during NRFO. Here, Acidovorax sp. BoFeN1, a typical NRFO bacterium, was used to investigate the Cd immobilization during NRFO at pH 7.0 with 0.1, 0.5, and 1.0 mg/L Cd, respectively. Higher initial Cd concentration resulted in a higher amount of Cd immobilized in precipitates, but showed stronger inhibition on nitrate reduction, acetate metabolism, and cell growth. The presence of Cd barely influenced the Fe(II) oxidation during NRFO or chemodenitrification, but retarded the mineral transformation to secondary crystalline minerals, i.e., lepidocrocite and goethite. The extracellular polymeric substances deposited in the bacteria-mineral precipitates were rich in tyrosine-like and tryptophan-like proteins with negatively charged amino and carboxyl groups. The STEM-HAADF images with EDX mapping demonstrated that Cd was strongly co-localized with Fe on the cell surface and in the periplasm. Cadmium immobilization experiments with bacterial cells or during chemodenitrification indicated that the bacterial cells and secondary minerals formed during chemodenitrification are comparably important for Cd immobilization in the Cd0.1 treatment, while the secondary minerals played a predominant role in Cd immobilization in the Cd0.5 and Cd1.0 treatments. These results suggested that Cd was likely associated with the secondary iron minerals, which precipitated with the proteins on the cell surface and in the periplasm. Our findings provide a comprehensive understanding of the roles of Cd, bacterial cells, and secondary minerals formed via chemodenitrification, as well as their interactions during the complicated NRFO process at circumneutral pH.

Analgesic Effect of the Lysine-Containing Short Peptide Is Due to Modulation of the NaV1.8 Channel Activation Gating System.

The present work continues our recent series of articles that aim to elucidate the ligand-receptor binding mechanism of short cationic peptides to the NaV1.8 channel in the nociceptive neuron. The applied methodological approach has involved several methods: the patch-clamp experimental evaluation of the effective charge of the NaV1.8 channel activation gating system, the organotypic tissue culture method, the formalin test, and theoretical conformational analysis. The lysine-containing short peptide Ac-KEKK-NH2 has been shown to effectively modulate the NaV1.8 channel activation gating system. As demonstrated by the organotypic tissue culture method, the studied short peptide does not trigger the downstream signaling cascades controlling neurite outgrowth and should not be expected to evoke adverse side effects. Conformational analysis of the Ac-KEKK-NH2 molecule has revealed that the distances between the positively charged amino groups of the lysine side chains are equal to 11-12 Å. According to the previously suggested mechanism of ligand-receptor binding of short peptides to the NaV1.8 channel molecule, Ac-KEKK-NH2 should exhibit an analgesic effect, which has been confirmed by the formalin test. The data obtained unequivocally indicate that the studied lysine-containing short peptide is a promising candidate for the role of a novel analgesic medicinal substance.

Fluorescence “Turn‐Off‐On” Detection of Heparin and Protamine Based on Bovine Serum Albumin‐Stabilized Carbon Dots (BSA‐CDs)

AbstractHeparin and protamine are two therapeutically significant biomolecules utilized in surgeries and extracorporeal therapy. Hence, real time monitoring of their concentration levels in body fluids is quite requisite. Herein, we developed, Bovine Serum Albumin stabilized carbon dots by a microwave‐assisted synthesis for the detection of heparin and protamine. Heparin has sulfate and carboxy groups that can interact with the positively charged surface amino groups of protamine through electrostatic interactions and hydrogen bonds. The blue fluorescence exhibited by BSA‐Carbon dots shows decrease in fluorescence emission on addition of negatively charged heparin. When cationic protein protamine is introduced to this system, the fluorescence is recovered due to electrostatic interaction with heparin. The system shows a Limit of detection (LOD) of 0.014 mM and 0.053 mM on addition of heparin and protamine respectively. The probe exhibited positive results with good selectivity and sensitivity towards other coexisting biomolecules and ions that appear in body fluids. The study was extended in biological matrix such as human serum and urine and found good recovery percentage in between 90–120%. The practical applicability was analyzed using a paper strip assay. Hence, a sensitive “turn‐off‐on” probe was effectively developed for the detection of heparin and protamine on a clinical basis.

Engineering of functional nanosnowflakes from gold nanocarriers capped with amino-modified DNA oligonucleotides.

The design, engineering and electron microscopic characterization of anisotropic nanosized snowflake-like structural assemblies (nanosnowflakes) is reported. They were fabricated through immobilization of double stranded amine-modified and thiol-terminated DNA oligonucleotides on the surface of ultra-small isotropic gold nanoparticles used as nanocarriers. The transmission electron microscopy images combined with spectrophotometric data revealed the formation of self-assembled structural aggregation between individual ligands-coated nanoparticles. They act as seeds for the further spontaneous dendritic growth in different directions. Their anisotropic morphology is formed due to the occurrence of facilitated electrostatic interactions between positive charged amino-groups and the negative sugar-phosphate backbone of oligonucleotides. Thus, nanosnowflakes with size distribution between 40 and 80 nm were obtained. The microscopic analysis demonstrated also that the stable nanosnowflakes structure was highly dependent on the solution ionic strength, which effect the charge fluctuation within the assembly. The reported DNA functionalized nanostructures have potential to be applied as a platform for development of therapeutic materials, as well as drug delivery nanosystems. RESEARCH HIGHLIGHTS: The engineering, fabrication, and microscopic characterization of DNA nanosnowflakes is reported. The electron microscopy analysis revealed formation of self-assemblies with anisotropic morphology. The nanosnowflakes size distribution was between 40 and 80 nm.

Facile and efficient preparation of amino bearing metal-organic frameworks-coated cotton fibers for solid-phase extraction of non-steroidal anti-inflammatory drugs in human plasma

The determination of blood concentration of non-steroidal anti-inflammatory drugs (NSAIDs) is highly desired in clinical practice. In this work, three amino bearing metal-organic frameworks (amino-MOFs) coated cotton fibers were prepared using a facile cysteine-triggered in situ growth strategy and proposed as in-tip solid-phase microextraction (in-SPME) adsorbents for efficient extraction of non-steroidal anti-inflammatory drugs from human plasma. The self-made adsorbents exhibited satisfactory extraction performance toward three NSAIDs including diclofenac sodium, ketoprofen and flurbiprofen. Under the optimized conditions, the established method exhibited satisfactory enrichment performance, low limits of detection and excellent extraction efficiency. Good reproducibility, wide linear range, excellent linearity and satisfactory sensitivity were obtained in the experiment. The method was also used for the enrichment and determination of NSAIDs in human plasma samples. Good recoveries were obtained, ranging from 66.5% to 98.9% with relative standard deviations less than 6.62%. The good performance of amino-MOFs was due to the synergistic effects arising from grafted charged amino groups within ordered pores of suitable size, leading to strong affinity towards guest molecules. Electrostatic interaction, hydrogen bond and π-π interaction played a vital role in the extraction of NSAIDs. This report indicated the potential of amino-MOFs as efficient adsorbents for the determination of NSAIDs from human plasma.

Interaction of G-quadruplex Forming DNA Aptamers with PAMAM Dendrimers Studied by Dynamic Light Scattering and UV-VIS Spectrophotometry.

The complexes of G-quadruplex forming DNA thrombin binding aptamers (TBA) and polyamidoamine dendrimers (PAMAM) were studied with the aim to form a model targeted drug delivery system. Hydrodynamic diameter, zeta potential and melting temperature (Tm ) were investigated by dynamic light scattering and UV-VIS spectrophotometry. Non-covalent adsorption by means of electrostatic interaction between positively charged amino groups of dendrimers (+) and negatively charged phosphate groups of aptamers (-) has driven the formation of aggregates. The size of complexes was in the range of 0.2-2 μm and depended on the type of dispersant, charge ratio (+/-) and temperature. Raising the temperature increased the polydispersity, new smaller size distributions were observed indicating the G-quadruplex unfolding. The melting transition temperature of TBA aptamer was affected by the presence of amino-terminated PAMAM rather than carboxylated succinic acid PAMAM-SAH dendrimer, thus supporting the electrostatic nature of interaction that disturbed denaturation of target-specific quadruplex aptamer structure.