Protonated Amino Groups Research Articles

Efficient removal of per/polyfluoroalkyl substances from water using recyclable chitosan-coated covalent organic frameworks: Experimental and theoretical methods

Covalent organic frameworks (COFs) demonstrate remarkable potential for adsorbing per/polyfluoroalkyl substances (PFAS). Nevertheless, the challenge of recycling powdered COFs hampers their practical application in water treatment. In this research, a quaternary amine COF with inherent positive surface charge was synthesised to adsorb perfluorooctanoic acid (PFOA) via electrostatic interactions. The COF was then combined with chitosan (CS) through a simple dissolution-evaporation process, resulting in a composite gel material termed COF@CS. The findings indicated that the adsorption capacity of COF@CS significantly surpassed that of the original COF and CS. According to the Langmuir model, COF@CS achieved a maximum PFOA capacity of 2.8 mmol g−1 at pH 5. Furthermore, the adsorption rate increased significantly to 6.2 mmol g−1 h−1, compared to 5.9 mmol g−1 h−1 for COF and 3.4 mmol g−1 h−1 for CS. Notably, COF@CS exhibited excellent removal efficacy for ten other types of PFAS. Moreover, COF@CS could be successfully regenerated using a mixture of 70% ethanol and 1 wt% NaCl, and it exhibited stable reusability for up to five cycles. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) characterisation, and theoretical calculations revealed that the quaternary amine functional group in COF served as the primary adsorption site in the composite gel material, while the protonated amino group on CS enhanced PFOA adsorption through electrostatic interaction. This study highlights the significant practical potential of COF@CS in the removal of PFAS from aqueous solution and environmental remediation.

Multifunctional composite materials of rGO with RAFT initiated polymers with terminal amine or protonated amine functionalities for chemical eliminations HCHO and acidic pollutants at ambient conditions

In this paper, the contribution of self-assembled composite material of bifunctional polymer prepared by RAFT polymerization and rGO to the removal of low concentration HCHO and acids from air were systematically studied. Experimental results demonstrate that the condensation reaction between HCHO and the protonated amino group at the terminal of the rGO-py-pAMHS-NH3+-ph chain effectively can eliminate HCHO chemically, resulting in the release of H2O as the sole by-product following oxime bonds formation. rGO alone is incapable of chemically removing gaseous HCHO, but when combined with the py-pAMHS-NH3+-ph, efficient HCHO conversion can be achieved, well elucidating the remarkable HCHO removal capability via rGO-py-pAMHS-NH3+-ph. The HCHO chemical removal performance of composite is evaluated by a self-made device at the 1000 mL/min N2 velocity under 25 °C and 50 % RH and it is found that 206.41 mg of HCHO can be removed in approximately 4 h by using 1.0 g of rGO-py-pAMHS-NH3+-ph. In addition, cycling experiments demonstrate the rGO-py-pAMHS-NH3+-ph possesses good durability. We also find that the rGO-py-pAMHS-NH2-ph has the ability to remove acids when the terminal protonated amino groups have been converted into amine functionalities. This green and zero-carbon emission methodology for chemical removal of HCHO degradation and acid pollutants could provide valuable reference for developing other efficient strategies to remove other pollutants such as VOCs etc.

Tuning of ion current rectification and ion current saturation of multiple nanochannels in polymeric membrane

The present study gives an insight into ion flow dynamics of aqueous electrolytes via functionalized multiple nanochannels in polyethylene terephthalate (PET) membrane. The selectivity of certain ions (anions/cations) of various electrolyte combinations KCl- KClO4 (S1), KBr-KCl (S2), KBr-KClO4 (S3) over their counter-ions by the nanochannels (generated via swift heavy ion irradiation followed by chemical etching) has been studied. Tuning of the ion transport and ion current rectification has been done using different functionalized nanochannels (with charged carboxyl and protonated amino groups). The impact of ion selectivity of the nanochannels is reflected in the short circuit current and ion current saturation of different systems. The collection of counter ions outside the channels along with the in-built potential due to the flow of ions inside the channels play a crucial role in the ion transport behaviour of the collective system. The cation-selective channels (with charged carboxyl groups) show low rectification ratio compared to the anion-selective channels. The functionalized nanochannels with two -OH polar charge groups (generated through the amino-silane based reagent (3-aminopropyl) trimethoxysilane (APTMS)) exhibit higher current saturation values (S1AP∼31 μA, S2AP∼30 μA and S3AP ∼ 30.5 μA) and higher short circuit current values (S1AP ∼32.3μA, S2AP ∼ 29.6μA and S3AP ∼31.3μA) due to the overlapping of electric double layer (EDL). Systematic study of tuning of ion transport through nanochannels helps to understand the nanofluidic flow and has imminent application in the fabrication of nanoelectronic and bioinspired nanodevices.

Inhibitory effect of microplastics derived organic matters on humification reaction of organics in sewage sludge under alkali-hydrothermal treatment

Alkali-hydrothermal treatment (AHT) of sewage sludge is often used to recover value-added dissolved organic matters (DOM) enriched with artificial humic acids (HA). Microplastics (MPs), as emerging contaminants in sewage sludge, can leach organic compounds (MP-DOM) during AHT, which potentially impact the characteristics of thermally treated sludge's DOM. This study employed spectroscopy and Fourier transform-ion cyclotron resonance mass spectrometry (FT-ICR-MS) to explore the impacts of MPs on DOM composition and transformation during AHT. The biological effects of DOM were also investigated by hydroponic experiments. The results showed that the leaching of MP-DOM led to a substantial increase in DOC content of DOM of thermally treated sludge. Conversely, the HA content significantly decreased in the presence of MPs, resulting in a decline of plant growth facilitation degree. FT-ICR-MS analysis revealed that the reduction in HA content was characterized by a notable decline in the abundance of O6–7 and N1–3O6–7 molecules. Reactomics results indicated that the leaching of MP-DOM inhibited the Maillard reaction but bolstered oxidation reactions. The inhibition of Maillard reaction, resulting in a decrease in crucial precursors (dicarbonyl compounds, ketoses, and deoxyglucosone), was responsible for the decrease of HA content. The primary mechanism responsible for inhibiting the Maillard reaction was the consumption of reactive amino reactants through two pathways. Firstly, the leaching of organic acids in MP-DOM caused decrease of sludge pH, leading to the protonation of amino groups. Secondly, the lipid-like compounds in MP-DOM underwent oxidation (-2H+O), producing fatty aldehydes that consumed the reactive amino reactants. These discoveries offer enhanced insights into the specific contribution of MPs to the composition, transformation, bioactivity of DOM during AHT process.

Effective adsorption and removal of Cr(VI) from wastewater using magnetic composites prepared by synergistic effect of polypyrrole and covalent organic frameworks

Cr(VI) as a toxic heavy metal can endanger human physical and mental health. The adsorption method has been widely used for Cr(VI) removal due to its advantages of cost-effectiveness and simplicity of operation. However, the key to Cr(VI) removal by adsorption lies in the construction of adsorption active sites. In this study, Fe3O4@COF-MT@PPy magnetic composites were prepared by the Schiff base method and in situ polymerisation to construct adsorbents with high specific surface area and abundant amino active sites for the removal of Cr(VI) from wastewater. The TEM and BET results showed that PPy was successfully encapsulated on the Fe3O4@COF-MT material, and the COF layer provided sites for the polymerisation of PPy, which resulted in a large specific surface area (400.93 m2/g) for Fe3O4@COF-MT@PPy, thus providing more adsorption sites. The VSM results showed that the prepared composites have good magnetic properties (13.8 emu/g) and are easy to separate from aqueous solutions. Encouragingly, the Fe3O4@COF-MT@PPy composites showed excellent adsorption performance for Cr(VI) in aqueous solution. The maximum adsorption capacity of the material for Cr(VI) was 429.18 mg/g at 298 K, which was much higher than Fe3O4@COF-MT with Fe3O4@PPy. Adsorption kinetics and isotherm analyses showed that the adsorption process was more in line with the pseudo-second-order and Langmuir models. The Fe3O4@COF-MT@PPy composites were able to maintain high adsorption capacity of Cr(VI) after five regenerations, which showed good reusability. In addition, interfering ion experiments demonstrated the selective adsorption of Fe3O4@COF-MT@PPy on Cr(VI). Using XPS for the analysis, it can be speculated that the adsorption mechanism is due to the abundant amino groups on the surface of the adsorbent firstly exerting electrostatic attraction and ion-exchange effect on the anion Cr(VI), and then the protonated amino groups reduce part of the Cr(VI) to Cr(III), and finally adsorb the Cr(III) on the surface of the material by chelation. Therefore, the recyclable Fe3O4@COF-MT@PPy has a good potential for adsorption of Cr-containing wastewater.

Selection, characterization, and biosensing applications of DNA aptamers targeting cyanotoxin BMAA.

Scientists have established a connection between environmental exposure to toxins like β-N-methylamino-l-alanine (BMAA) and a heightened risk of neurodegenerative disorders. BMAA is a byproduct from certain strains of cyanobacteria that are present in ecosystems worldwide and is renowned for its bioaccumulation and biomagnification in seafood. The sensitivity, selectivity, and reproducibility of the current analytical techniques are insufficient to support efforts regarding food safety and environment monitoring adequately. This work outlines the in vitro selection of BMAA-specific DNA aptamers via the systematic evolution of ligands through exponential enrichment (SELEX). Screening and characterization of the full-length aptamers was achieved using the SYBR Green (SG) fluorescence displacement assay. Aptamers BMAA_159 and BMAA_165 showed the highest binding affinities, with dissociation constants (Kd) of 2.2 ± 0.1 μM and 0.32 ± 0.02 μM, respectively. After truncation, the binding affinity was confirmed using a BMAA-conjugated fluorescence assay. The Kd values for BMAA_159_min and BMAA_165_min were 6 ± 1 μM and 0.63 ± 0.02 μM, respectively. Alterations in the amino proton region studied using solution nuclear magnetic resonance (NMR) provided further evidence of aptamer-target binding. Additionally, circular dichroism (CD) spectroscopy revealed that BMAA_165_min forms hybrid G-quadruplex (G4) structures. Finally, BMAA_165_min was used in the development of an electrochemical aptamer-based (EAB) sensor that accomplished sensitive and selective detection of BMAA with a limit of detection (LOD) of 1.13 ± 0.02 pM.

Wetting and swelling behaviour of N-acetylated thin chitosan coatings in aqueous media

Chitosan nanocoatings (thickness range of 120–540 nm) were produced on glass, zinc and silicon substrates with dip-coating and spin coating techniques to study their pH-dependent wetting and swelling behaviour. The coatings were N-acetylated with the methanolic solution of acetic anhydride to increase the degree of acetylation from 36 % to 100 % (according to ATR-FTIR studies). The measured contact angles of Britton–Robinson (BR) buffer solutions (pH 6.0, 7.4 and 9.0) were lower on the acetylated surfaces (ca. 50°), than that of their native counterparts (ca. 70°) and does not depend on the pH. Contrary, contact angles on the native coating deteriorated 10°-15° with increasing the pH. In addition, for native coatings, the decrease of the contact angles over time also showed a pH dependence: at pH 9.0 the contact angle decreased by 7° in 10 min, while at pH 6.0 it decreased by 13° and at a much faster rate. The constraint swelling of the coatings in BR puffer solutions was studied in situ by scanning angle reflectometry. The swelling degree of the native coatings increased significantly with decreasing pH (from 250 % to 500 %) due to the increased number of protonated amino groups, while the swelling degree of acetylated coatings was ca. 160 % regardless of the pH. The barrier properties of the coatings were studied by electrochemical tests on zinc substrates. The analysis of polarization curves showed the more permeable character of the acetylated coatings despite the non-polar character of the bulk coating matrix. It can be concluded that in the case of native coatings, 49 % of the absorbed water is in bound form, which does not assist ion transport, while in the case of acetylated coatings, this value is only 33 %.

Role of amino acid functional group in alga-amino acid-Zn ternary complexes

The bioaccumulation of heavy metals (HMs) at the water-algal interface determines their threat degree to aquatic ecosystem. Amino acids (AAs), as predominant components of dissolved organic matter (DOM), play pivotal roles in shaping the speciation of HMs in water and their subsequent accumulation by algae. However, the diverse nature of amino acid poses a challenge in generalizing the underlying mechanisms. This study explores four amino acids (asparagine, aspartic acid, glycine, lysine), each possessing distinct amino and carboxyl groups, and investigates their impact on zinc (Zn) bioaccumulation through batch experiments. Upon the introduction of AAs, the adsorption process obeyed the pseudo-second-order kinetic adsorption model demonstrating chemisorption (R2 >0.99), and it affected Zn externalization (up to 3.994 mmol g-1). This phenomenon followed a two-step model, indicating multilayer adsorption. The study proposed that the protonated amino group of AA could serve as a link between Zn-AA complex and microalgae. Amino acids adsorbed onto the surface of microalgae via protonated amino groups did not occupy the Zn-binding sites, instead, they furnished additional functional groups. This differs from the previous results of organic acids containing only carboxyl functional groups as DOM. Multiple linear regression equations and correlation analyses were used to explain the effects of amino and carboxyl morphology on microalgae accumulation of Zn. The equation showed that the leading model terms explain 75.8% of the accumulation amount variance. This study enhances our understanding of the effects of functional group-different DOM on the accumulation of heavy metals in microalgae, offering insights for future research and prediction.

Equilibrium of sorption of Tribulus Terrestris steroid saponins on a natural polymer sorbent – chitosan

Steroidal saponins have a wide spectrum of pharmacological action and therefore are widely used in pharmacological practice. Chitosan is a unique material. Its biocompatibility, biodegradability, non-toxicity, as well as its cationic nature reveal the potential of this biopolymer as a carrier of drugs for their targeted delivery. The immobilization of biologically active substances can be carried out in a variety of ways - nanomicelles with an encapsulated drug or their polyelectrolyte complexes with oligochitosans, depending on the nature of the active substance. The study of the sorption of saponins by chitosan under equilibrium conditions was studied. An analysis of the equilibrium curves of sorption of Tribulus Terrestris saponin on chitosan was carried out. The presence of a local minimum on the isotherm in the region of solution concentrations corresponding to micellization was revealed. It has been established that the course of the saponin sorption isotherm is determined by competing association processes in a solution and on the surface of chitosan. The pH of the solution did not change, which indicated the absence of ionic interactions involving the protonated amino group of chitosan. The moisture content of chitosan during the sorption of saponin was studied. The antibatic nature of the absorption curves and moisture content curves of chitosan was revealed. An analysis of the saponin sorption isotherm was carried out using the adsorption theories of Langmuir, Freundlich, and BET. High values of the correlation coefficients allowed us to use the Freundlich equation for a quantitative description of the isotherm in the initial section, and to analyse the entire isotherm using the BET theory, which takes into account the polymolecular nature of sorption. The results obtained for the description of the sorption isotherm of saponin were consistent with the proposed mechanism of its absorption by chitosan. Using IR spectroscopy, it was established that the interaction in the sorbent-sorbate system was due to the emerging hydrogen bonds between the amino and hydroxyl groups of chitosan and the hydroxyl groups of saponin carbohydrates. The results obtained, as well as literature data, confirm the formation of cavities in polysaccharides into which saponin is “incorporated”. In our case, the presence of cavities formed by seven monomer fragments of chitosan, the stability of which is fixed by hydrogen bonds was discussed.

Development of Chitosan/Sodium Carboxymethylcellulose Complexes to Improve the Simvastatin Release Rate: Polymer/Polymer and Drug/Polymer Interactions' Effects on Kinetic Models.

Simvastatin (SIM) is a potent lipid-lowering drug used to control hyper-cholesterolemia and prevent cardiovascular diseases. SIM presents low oral bioavailability (5%) because of its low aqueous solubility. In this work, polyelectrolyte complexes (PEC) are developed with different chitosan (CS) and carboxymethylcellulose (CMC) ratios that will allow for an increase in the SIM dissolution rate (2.54-fold) in simulated intestinal medium (pH 4.5). Scanning Electron Microscopy (SEM) images revealed highly porous structures. The changes between both complexes, PEC-SIM:CS:CMC (1:1:2) and (1:2:1), were related to the relaxation of the polymer chains upon absorption of the dissolution medium. Fourier-transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and powder X-ray diffraction (XRPD) studies were used to evaluate the polymer/polymer and drug/polymer interactions on the different PEC-SIM:CS:CMC ratios. In addition, the PEC-SIM:CS:CMC (1:2:1) complex exhibited a high ratio of protonated amino groups (NH3+) and an increase in intramolecular hydrogen bonds, which were correlated with a high expansion of the interpolymer chains and an increase in the SIM dissolution rate. Different kinetic models such as zero-order, first-order, Higuchi and Korsmeyer-Peppas were studied to evaluate the influence of CS/CMC ionic interactions on the ability to improve the release rate of poorly soluble drugs.

The Photoprotective Protein PsbS from Green Microalga Lobosphaera incisa: The Amino Acid Sequence, 3D Structure and Probable pH-Sensitive Residues.

PsbS is one of the key photoprotective proteins, ensuring the tolerance of the photosynthetic apparatus (PSA) of a plant to abrupt changes in irradiance. Being a component of photosystem II, it provides the formation of quenching centers for excited states of chlorophyll in the photosynthetic antenna with an excess of light energy. The signal for "turning on" the photoprotective function of the protein is an excessive decrease in pH in the thylakoid lumen occurring when all the absorbed light energy (stored in the form of transmembrane proton potential) cannot be used for carbon assimilation. Hence, lumen-exposed protonatable amino acid residues that could serve as pH sensors are the essential components of PsbS-dependent photoprotection, and their pKa values are necessary to describe it. Previously, calculations of the lumen-exposed protonatable residue pKa values in PsbS from spinach were described in the literature. However, it has recently become clear that PsbS, although typical of higher plants and charophytes, can also provide photoprotection in green algae. Namely, the stress-induced expression of PsbS was recently shown for two green microalgae species: Chlamydomonas reinhardtii and Lobosphaera incisa. Therefore, we determined the amino acid sequence and modeled the three-dimensional structure of the PsbS from L. incisa, as well as calculated the pKa values of its lumen-exposed protonatable residues. Despite significant differences in amino acid sequence, proteins from L. incisa and Spinacia oleracea have similar three-dimensional structures. Along with the other differences, one of the two pH-sensing glutamates in PsbS from S. oleracea (namely, Glu-173) has no analogue in L. incisa protein. Moreover, there are only four glutamate residues in the lumenal region of the L. incisa protein, while there are eight glutamates in S. oleracea. However, our calculations show that, despite the relative deficiency in protonatable residues, at least two residues of L. incisa PsbS can be considered probable pH sensors: Glu-87 and Lys-196.

In Ukrainian

Regulation of enterohepatic circulation of bile acids in human body is actual task to overcome cardiovascular diseases. The aim of this work was to create biocompatible sorbents with improved sorption ability in relation to bile acids. Mesoporous organosilicas of MCM‑41 type with chemically grafted 3‑aminopropyl and steroid groups were obtained by sol‑gel condensation of tetraethyl orthosilicate and functional silanes in the presence of template cetyltrimethylammonium bromide. Porous structure of synthesized organosilicas was characterized by low‑temperature nitrogen adsorption–desorption and X‑ray diffraction analysis. Formation of typical for MCM‑41 hexagonal arrangement of cylindrical mesopores was confirmed. Structural parameters of synthesized silica materials were calculated. The influence of surface steroid groups on sorption ability of organosilicas was studied on example of bile salts (sodium cholate and taurocholate) in dependence of duration of contact, acidity of medium, and equilibrium concentration. Analysis of kinetic parameters of sorption estimated by Lagergren and Ho-McKey models confirms the proceeding of pseudo-second order process. The most effective sorption of sodium cholate and taurocholate was observed at pH ~ 5 and pH ~ 2, respectively, where the ovterlapping of pH regions of 3‑aminopropyl groups protonation and bile acids dissociation takes place. Analysis of experimentally obtained isotherms by use of Freundlich, Redlich‑Peterson, and BET models was carried out. It has been found that protonated amino groups are the main sorption centers of bile acids protolytic forms by synthesized aminosilica in pH range from 1 to 8. Introduction of steroid groups in surface layer at sol-gel synthesis leads to the increase of bile salts sorption due to the cooperative interactions with formation of supramolecular structures in the surface layer of organosilica. Obtained results prove prospects of usage of organosilica sorbents with surface steroid groups for regulation of bile acids content in human body.

Sustainable remediation of toxic congo red dye pollution using bio based carbon nanocomposite: Modelling and performance evaluation

Remediation of synthetic dyes found in aqueous environment poses a serious challenge for treatment due to their resistance to chemical and biological degradation. This research study investigated the application of Chitosan-ZnO-Seaweed bio nanocomposite in the remediation of congo red. The novel bionanocomposite was characterised by FTIR, SEM, TEM, EDS and XRD studies. The FTIR spectra and SEM images indicated the adsorption of congo red onto the synthesized bionanocomposite. The batch wise experimental studies were done to explore the influence of process variables on removal of congo red from synthetic wastewater and to determine optimized conditions. Under optimized conditions of pH 3, temperature 40 °C, initial congo red concentration 50 mg/L, bionanocomposite quantity 0.03 g/L and interaction period 30 min, the bionanocomposite removed 95.64% of congo red. Thermodynamic studies were carried out and the parameters, ΔH° and ΔS° were found to be 38.386 kJ/mol and 0.1451 kJ/mol. K, respectively. The isotherm and kinetic study showed that monolayer Langmuir model was obeyed (R2 = 0.968) and the experimental value of congo red adsorption correlated well with pseudo second order model (R2 = 0.9938) respectively. The maximum adsorption capacity was found to be 303.03 mg/g. Protonated amino group of chitosan, hydroxyl group of seaweed accounts for congo red adsorption along with zinc oxide.

Tunable Fungal Monofilaments from Food Waste for Textile Applications.

A fungal biorefinery is presented to valorize food waste to fungal monofilaments with tunable properties for different textile applications. Rhizopus delemar is successfully grown on bread waste and the fibrous cell wall is isolated. A spinnable hydrogel is produced from cell wall by protonation of amino groups of chitosan followed by homogenization and concentration. Fungal hydrogel is wet spun to form fungal monofilaments which underwent post-treatments to tune the properties. The highest tensile strength of untreated monofilaments is 65MPa (and 4% elongation at break). The overall highest tensile strength of 140.9MPa, is achieved by water post-treatment. Moreover, post-treatment with 3% glycerol resulted in the highest elongation % at break, i.e., 14%. The uniformity of the monofilaments also increased after the post-treatments. The obtained monofilaments are compared with commercial fibers using Ashby's plots and potential applications are discussed. The wet spun monofilaments are located in the category of natural fibers in Ashby's plots. After water and glycerol treatments, the properties shifted toward metals and elastomers, respectively. The compatibility of the monofilaments with human skin cells is supported by a biocompatibility assay. These findings demonstrate fungal monofilaments with tunable properties fitting a wide range of sustainable textiles applications.

Quantum chemical analysis of isomerization and protonation of amino group in D-glucosamine

Quantum chemical analysis of isomerization and protonation of amino group in D-glucosamine

Efficient adsorption and in-situ ceramics immobilization of simulated trivalent actinides (Nd) by amino-functionalized mesoporous zirconia-silica

It is of great significance to develop a kind of adsorbent which can adsorb and in-situ immobilize radionuclides from aqueous solution. Herein, new amino-functionalized mesoporous zirconia-silica (ZNSi) composites were prepared and applied to adsorb and in-situ immobilize the simulated trivalent actinides (Nd) from aqueous solution. The obtained ZNSi composites exhibited high Nd adsorption capacity (31.14 mg/g) owing to the formation of Nd(OH)3 via the reaction between Nd3+ and OH− derived from the protonation of amino groups. The spent adsorbents with adsorbed Nd3+ were successfully changed to stable ZrSiO4-based glass ceramics by simple sintering treatment. The ZrO2 and Nd contents had great effect on the phase composition, microstructure evolution and aqueous stability of the obtained ZrSiO4-based glass ceramics waste forms. The immobilized Nd showed excellent aqueous stability (10−7 g m−2 d−1) due to the crystal lattice immobilization of ZrSiO4. Owing to the efficient adsorption and in-situ immobilization ability, the obtained ZNSi could be potential materials for radioactive wastewater treatment.

Cr-based metal–organic frameworks (MOFs) with high adsorption selectivity and recyclability for Au (Ⅲ): Adsorption behavior and mechanism study

Preparation of efficient adsorbents is of great significance for the recovery of precious metals from secondary resources. Herein, –NH2 was successfully grafted on MIL-101(Cr) via hydrothermal reaction to improve the adsorption capacity of Au (Ⅲ) in aqueous solution. MIL-101(Cr)–NH2 had a huge specific surface area (1016.50 m2‧g−1), which can provide more adsorption sites for Au (III). At 298 K, the maximum adsorption capacity of Au (III) by MIL-101(Cr)–NH2 was 792.43 mg∙g−1 and was higher than that by MIL-101(Cr) (140.83 mg∙g−1). The adsorption data was well fitted by Langmuir and pseudo-second-order models, confirming that the adsorption process conformed to single molecule adsorption and chemical adsorption. Mechanism study indicated that the adsorption of Au (III) by MIL-101(Cr)–NH2 was initiated with electrostatic attraction and promoted by reduction and inner complexation between AuCl4- and protonated amino groups. During adsorption, Au (Ⅲ) was reduced to Au (0) and Au (I) by –NH2. Density functional theory (DFT) calculation demonstrated that MIL101(Cr)–NH2 possessed higher binding affinity and more adsorption sites for Au (III) than MIL-101(Cr). Moreover, MIL-101(Cr)–NH2 exhibited excellent selectivity towards Au (III) and good recyclability, which is promising in the recovery of precious metals.

Physicochemical evaluation of chitosan–xanthan gum nanoemulsions as polyunsaturated enriched lipid–carrier

Polyunsaturated enriched lipid–carriers have been drawn attention due to their health benefits. This work aimed to develop new delivery carriers based on chitosan–xanthan gum nanoemulsions with tuna oil, which is rich in eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA). Therefore, it was intended to elucidate the physicochemical interactions within chitosan–xanthan gum–polyunsaturated fatty acids nanoemulsions. The droplets size, zeta potential, rheological and thermal characteristics, as well as the kinetic, thermodynamic and oxidative studies of the nanoemulsions were performed. All emulsions presented droplet sizes in the nanoscale range (around 224–289 nm) and a pseudoplastic rheological behavior. Thermodynamic parameters showed that the viscous flows of all nanoemulsions were nonspontaneous and exothermic, presenting a more orderly state. However, increased xanthan gum concentration resulted in endothermic viscous flow. Based on the results, protonated amino groups from chitosan improved electrostatic stability due to an increase in zeta potential values, while the enhanced viscosity led to by xanthan gum reduced the diffusivity of dissolved oxygen and increased oxidative stability. Moreover, electrostatic interactions between chitosan and xanthan gum increased the steric and oxidative stabilities of nanoemulsions.

Development of Riluzole Analogs with Improved Use-Dependent Inhibition of Skeletal Muscle Sodium Channels.

Several commercially available and newly synthesized riluzole analogs were evaluated in vitro as voltage-gated skeletal muscle sodium-channel blockers. Data obtained from the patch-clamp technique demonstrated that potency is well correlated with lipophilicity and the introduction of a protonatable amino function in the benzothiazole 2-position enhances the use-dependent behavior. The most interesting compound, the 2-piperazine analog of riluzole (14), although slightly less potent than the parent compound in the patch-clamp assay as well as in an in vitro model of myotonia, showed greater use-dependent Nav1.4 blocking activity. Docking studies allowed the identification of the key interactions that 14 makes with the amino acids of the local anesthetic binding site within the pore of the channel. The reported results pave the way for the identification of novel compounds useful in the treatment of cell excitability disorders.

Gas-Phase Internal Proton-Transfer of Protonated para-Aminobenzoic Acid Catalyzed by One Methanol Molecule.

Electrospray ionization (ESI) is used to deliver analytes for mass analysis across a huge range of mass spectrometry applications. Despite its ubiquitous application and many mechanistic investigations, it remains that a fundamental understanding of ESI processes is not complete. In particular, all the factors that influence the populations of protonation isomers are elusive such that it remains a challenge to optimize experimental conditions to favor one isomer over another. The molecule para-aminobenzoic acid has emerged as an archetype for the study of protonation isomers, with both amino and carboxylic acid protonation site isomers (protomers) typically formed upon ESI, with the isomer ratio shown to be sensitive to several physical and chemical parameters. Here we report an ion-trap mass spectrometry study of the time-resolved methanol-catalyzed proton transfer between the amine and carboxylic acid moieties of para-aminobenzoic acid. The experimental and computational results presented are consistent with a bimolecular mechanism where isomerization is mediated by a single methanol rather than a multimolecular Grotthuss proton transfer process. Pseudo-first-order rate constants for protomer specific product ions are reported and confirm the depletion of the amino protomer is correlated to the growth of the carboxylic acid protomer. Under the controlled conditions of a low-pressure ion-trap mass spectrometer (2.5 mTorr, 300 K), the number of methanol molecules required to isomerize para-aminobenzoic acid is determined to be one, and the second-order rate constant for methanol-catalyzed isomerization is (1.9 ± 0.1) × 10-11 cm3 molecule-1 s-1. The para-aminobenzoic acid vehicle mechanism is explored computationally at the DSD-PBEP86-D3BJ/aug-cc-pVDZ level of theory and reveals that the transition state for proton transfer is submerged (-10 kJ mol-1) relative to the separated reactant energies. The findings from this paper show that single-solvent catalyzed intramolecular proton transfer reactions are possible and must be considered during the late stages of ESI to predict the site(s) of protonation and the ion's stability in the presence of solvent molecules.