Nonionic Compounds Research Articles

Synthesis and cytotoxicity of copper(II) semicarbazone complexes with lipophilic counter-anions

A series of (2,4-dihydroxybenzaldehyde dibenzyl semicarbazone) perfluoroalkyl carboxylato copper(II) complexes, [CF3(CF2)nCO2(LH)Cu] (LH2 = 2,4-dihydroxybenzaldehyde dibenzyl semicarbazone; n = 0, 2, 4, 6; 1–4), and (2,4-dihydroxybenzaldehyde dibenzyl semicarbazone) pyridine copper(II) perfluoroalkyl carboxylates, [(LH)(py)Cu]+[CF3(CF2)nCO2]− (5–8) were synthesized. The lipophilicity of these compounds was determined by reverse-phase thin layer chromatography and correlated with their cytotoxicity towards MOLT-4 human leukaemia cells. Cytotoxicity is more strongly correlated with lipophilicity for the non-ionic compounds (1–4) than for the ionic compounds (5–8). Compounds 5–8 (IC50 2.8–3.8 μM) are generally more cytotoxic than compounds 1–4 (IC50 3.6–8.4 μM). They also exhibit slightly higher cytotoxicity than the parent anticancer compound [(LH)(py)Cu]+[NO3]− (IC50 4.15 μM), suggesting that it is possible to enhance the cytotoxicity of [(LH)(py)Cu]+[NO3]− by replacing nitrate with anions of higher lipophilicity. Attempts to synthesize the non-fluorinated analogue [(LH)(py)Cu]+[CH3CO2]− resulted in the formation of the deprotonated complex [L(py)Cu], whose structure was confirmed by X-ray crystallography. The structural parameters indicate that the deprotonation site is the hydrazonic nitrogen of the semicarbazone ligand.

Miniaturized flexible micro-tube plasma ionization source for the effective ionization of non-easily ionizable pesticides in food with liquid chromatography/mass spectrometry

In this article, we have studied the potential of flexible microtube plasma (FμTP) as ionization source for the liquid chromatography high-resolution mass spectrometry detection of non-easily ionizable pesticides (viz. nonpolar and non-ionizable by acid/basic moieties). Phthalimide-related compounds such as dicofol, dinocap, o-phenylphenol, captan, captafol, folpet and their metabolites were studied. Dielectric barrier discharge ionization (DBDI) was examined using two electrode configurations, including the miniaturized one based on a single high-voltage (HV) electrode and a virtual ground electrode configuration (FμTP), and also the two-ring electrode DBDI configuration. Different ionization pathways were observed to ionize these challenging, non-easily ionizable nonpolar compounds, involving nucleophilic substitutions and proton abstraction, with subtle differences in the spectra obtained compared with APCI. An average sensitivity increase of 5-fold was attained compared with the standard APCI source. In addition, more tolerance with matrix effects was observed in both DBDI sources. The importance of the data reported is not just limited to the sensitivity enhancement compared to APCI, but, more notably, to the ability to effectively ionize nonpolar, late-eluting (in reverse-phase chromatography) non-ionizable compounds. Besides o-phenylphenol ([M − H]-), all the parent species were efficiently ionized through different mechanisms involving bond cleavages through the effect of plasma reagent species or its combination with thermal degradation and subsequent ionization. This tool can be used to figure out overlooked nonpolar compounds in different environmental samples of societal interest through non-target screening (NTS) strategies.

Utilization of polymeric binders to agglomerate oxidized copper ore

Permeability reduction is a major challenge in heap leaching, primarily caused by the accumulation of fines that move with the leaching agent, leading to the formation of dead zones and channeling within the heap. In the Aria copper beneficiation plant, the 0–2 mm fraction with a copper grade of 1.4% undergoes pre-separation prior to heap loading without further processing. This study investigated the potential of using the agglomeration method to improve permeability in the case of using the 0–2 mm fraction of ore. Mineral compounds, such as sodium silicate and calcium sulfate, and non-ionic, cationic, and anionic polymer compounds, were used in the agglomeration process. The strength of interparticle bonding was evaluated by measuring the fine migration percentage (FMP) in the soak test. The results revealed that agglomerates produced using non-ionic compounds had the highest bonding strength, with an FMP of 3.89%, the lowest of all the compounds tested. This enhanced bonding strength was attributed to the combined influence of hydrogen bonding forces and van der Waals forces.

Influence of Synthesis Conditions on the Properties of Zinc Oxide Obtained in the Presence of Nonionic Structure-Forming Compounds.

This work investigated the influence of synthesis conditions, including the use of nonionic structure-forming compounds (surfactants) with different molecular weights (400-12,600 g/mol) and various hydrophilic/hydrophobic characteristics, as well as the use of a glass substrate and hydrothermal exposure on the texture and structural properties of ZnO samples. By X-ray analysis, it was determined that the synthesis intermediate in all cases is the compound Zn5(OH)8(NO3)2∙2H2O. It was shown that thermolysis of this compound at 600 °C, regardless of the physicochemical properties of the surfactants, leads to the formation of ZnO with a wurtzite structure and spherical or oval particles. The particle size increased slightly as the molecular weight and viscosity of the surfactants grew, from 30 nm using Pluronic F-127 (MM = 12,600) to 80 nm using Pluronic L-31 (MM = 1100), PE-block-PEG (MM = 500) and PEG (MM = 400). Holding the pre-washed synthetic intermediates (Zn5(OH)8(NO3)2∙2H2O) under hydrothermal conditions resulted in the formation of hexagonal ZnO rod crystal structures of various sizes. It was shown that the largest ZnO particles (10-15 μm) were observed in a sample obtained during hydrothermal exposure using Pluronic P-123 (MM = 5800). Atomic adsorption spectroscopy performed comparative quantitative analysis of residual Zn2+ ions in the supernatant of ZnO samples with different particle sizes and shapes. It was shown that the residual amount of Zn2+ ions was higher in the case of examining ZnO samples which have spherical particles of 30-80 nm. For example, in the supernatant of a ZnO sample that had a particle size of 30 nm, the quantitative content of Zn2+ ions was 10.22 mg/L.

Investigation and elimination of surfactant-induced interferences in anodic stripping voltammetry for the determination of trace amounts of cadmium

This article aims to investigate in detail to what extent surfactants affect the determination of cadmium by anodic stripping voltammetry. In recent years, the production and use of surfactants have been steadily increasing, so that their concentration in environmental water samples is rising. At the same time, it is known that organic compounds, such as surfactants, often hinder the voltammetric determination of trace elements by stripping. Non-ionic (Triton X-100, Brij 35, Tween 20, Tween 60, Tween 80), cationic (CTAB, CTAC, DTAB, HPC) and anionic (DSS, SDS) compounds were selected to investigate the effect of surfactants on the voltammetric signal of cadmium. At the same time, the extent to which the addition of Amberlite resins to the analysed solution eliminates the interfering effect of surfactants was tested. Three types of Amberlite resins XAD-2, XAD-7 and XAD-16 were selected for the study and the ratio of resin weight to solution volume was determined. Finally, the determination of cadmium in surfactant-enriched environmental samples was carried out. The recoveries obtained between 95.5 and 107%, with RSD between 3.4 and 6.2%, confirm the validity and correctness of the proposed procedure All measurements were carried out by anodic stripping voltammetry using a CNTs/SGC electrode modified with a bismuth film as the working electrode.

Delayed hypersensitivity reactions to iodinated contrast media: A diagnostic approach by skin tests.

Adverse drug reactions to iodinated contrast media (ICM) have risen due to their increasing use in x-ray-based imaging modalities. Delayed hypersensitivity reactions are mainly caused by nonionic monomeric compounds and represent an issue impacting the diagnostic-therapeutic pathways of cancer, cardiology and surgery patients. To prospectively evaluate the usefulness of skin tests in delayed hypersensitivity reactions to ICM and to evaluate the tolerability of iobitridol, a monomeric nonionic low osmolality compound, as a possible safe alternative. Patients with delayed hypersensitivity reactions to ICM referred to us from 2020 to 2022 were prospectively enrolled in the study. All patients underwent patch test and, if negative, intradermal test with the culprit ICM and iobitridol as alternative. A total of 37 patients (females 24, 64.9%) were enrolled in the study. Iodixanol and iomeprol were the most frequently involved ICM (48.5% and 35.2%, respectively); 62.2% of patients presented maculopapular eruption, while 37.8% reported delayed urticaria-like rash. Skin tests resulted positive to the culprit ICM in 19 patients (51.4%), 16 to patch test and 3 to intradermal test. Skin tests with iobitridol, tested as alternative, resulted positive in 3/19 patients (15.8%). All 16 patients with negative results to iobitridol were administered this ICM and tolerated it. In at least half of patients, delayed-type hypersensitivity was demonstrated by skin tests, particularly by patch test. This diagnostic approach resulted simple, cost-effective and safe, not only to confirm the culprit ICM but also to identify iobitridol as feasible alternative.

Recalibrating polyparameter linear free energy relationships and reanalyzing mechanisms for partition of nonionic organic compounds to low-density polyethylene passive sampler

Equilibrium passive sampling techniques based on the low-density polyethylene (LDPE) film are increasingly used for determining the concentration of contaminants in water and air. Reliable models capable of predicting LDPE–water and LDPE–air partition coefficients (KiLDPEw and KiLDPEa) would be very useful. In previous studies, polyparameter linear free energy relationships (PP-LFERs) based on Abraham's solute descriptors were calibrated for LDPE–water and LDPE–air systems. Unfortunately, a portion of unreliable partition coefficients and solute descriptors were included in the calibration sets of these previous studies, leading to unexpected system parameters and predictive performance in the regression results. In this study, more reliable PP-LFERs were recalibrated for LDPE–water and LDPE–air systems (20‒25 °C) using carefully collected reliable partition coefficients and solute descriptors of various polar and nonpolar compounds (over one hundred and with low redundancy) from the literature, as well as the robust regression method. The PP-LFERs performed well with root-mean-square errors of 0.15–0.25 log units and successfully predicted KiLDPEw and KiLDPEa values spanning over 10 orders of magnitude for compounds with reliable descriptors. The partitioning mechanisms of compounds to LDPE were also reanalyzed and compared in detail with n-alkanes (C6–C16). Generally, LDPE is more prone to form dispersion interactions with solutes than n-alkanes, while it is more difficult to form cavities in LDPE. In addition, the crystallinity of LDPE is not the sole reason for the distinct constant terms presenting in PP-LFERs for LDPE–water and n-hexadecane–water systems.

Selective extraction of levoglucosan and its isomers from complex matrices using ligand exchange-solid phase extraction for analysis by liquid chromatography-electrospray ionization-tandem mass spectrometry

The analysis of trace quantities of monosaccharide anhydrides (MAs) in sediments is complicated by the lack of fast and reliable technologies to selectively extract these water-soluble non-ionic compounds from samples of complex composition. Here we describe a solid phase extraction method that takes advantage of the affinity between monosaccharide anhydrides (MAs) and immobilized Na+ ions related to ligand-exchange processes (LE-SPE). The capacity factor of LE-SPE columns was enhanced by using non-aqueous mobile phases such as DCM/MeOH mixtures. We have used the unique properties of LE-SPE columns to selectively extract MAs from lacustrine, coastal, and deep-sea oceanic sediment samples. The analytical procedure produces extracts with low ion suppression effects (0-20%), resulting in ideal conditions for MAs quantification with LC-ESI-MS/MS systems irrespective of the sedimentary matrix and MAs concentration. The analytical method yields repeatable concentration values (RSD of 9-23% for levoglucosan and 15-34% for mannosan and galactosan) and an IS recovery of 45-70%. The instrumental dynamic range is 10-10000 pg injected, but in practice, the methodological lower limit of quantification is constrained by sample contamination during processing. The combination of LE-SPE and LC-ESI-MS/MS has the potential to produce sensitive and reliable technologies to analyze saccharides and amino acids in environmental and biological samples.

A machine learning based approach for estimating site-specific partition coefficient Kd of organic compounds: Application to nonionic pesticides

The partitioning coefficient Kd for a specific compound and location is not only a key input parameter of fate and transport models, but also critical in estimating the safety environmental concentration threshold. In order to reduce the uncertainty caused by non-linear interactions among environmental factors, machine learning based models for predicting Kd were developed in this work based on literature datasets of nonionic pesticides including molecular descriptors, soil properties, and experimental settings. The equilibrium concentration (Ce) values were specifically included for the reason that a varied range of Kd corresponding to a given Ce occurred in a real environment. By transforming 466 isotherms reported in the literature, 2618 paired equilibrium concentrations of liquid-solid (Ce-Qe) data points were obtained. Results of SHapley Additive exPlanations revealed that soil organic carbon, Ce, and cavity formation were the most important. The distance-based applicability domain analysis was conducted for the 27 most frequently used pesticides with 15952 pieces of soil information from the HWSD-China dataset by setting three Ce scenarios (i.e., 10, 100, and 1000 μg L−1). It was revealed the groups of compounds showing log Kd < 0.06 and log Kd > 1.19 were composed mostly of those with log Kow of −0.800 and 5.50, respectively. When log Kd varied between 0.100 and 1.00, it was impacted by interactions among soil types, molecular descriptors, and Ce comprehensively, which accounted for 55% of the total 2618 calculations. It could be concluded that site-specific models developed in this work are necessary and practicable for the environmental risk assessment and management of nonionic organic compounds.

LITHIUM EXTRACTION FROM SPENT LITHIUM-ION BATTERIES WITH GREEN SOLVENTS: COSMO-RS MODELING

Lithium-ion batteries (LIBs) wide usage constitutes a disposal threat to the environment. As a result, several laws are being introduced to encourage the recycling of this waste, particularly, in lithium recovery. Deep eutectic solvent (DES) has been reported as an efficient solvent in valuable metal recovery from spent LIB. However, efficient deep eutectic solvent design requires a smart selection of components. This study developed a COSMO-RS model to screen several components as DES starting material in lithium extraction from spent LIB. The model consists of 188 different constituents. The model is developed using the cosmo therm software in the LIB application for the first time. The model uses lithium chemical potential to measure the affinity of lithium in the screened components. Overall, all the compounds show an affinity for lithium. The components are classified into ionic and non-ionic. The ionic compounds performed better than the non-ionic compounds. This is due to the coordinating ability of the ionic compounds’ cations with lithium. Further, this study highlights other properties such as reducibility, toxicity, and viscosity as screening strategies in DES component selection for lithium extraction. This is to implement the full green chemistry principle essential for industrial application. Keywords: Lithium-ion battery; Lithium; green technology; Deep eutectic solvents; COSMO-RS.

Mechanistic insight into adsorptive removal of ionic NOR and nonionic DEP organic contaminates by clay-biochar composites

The synthesis of clay-biochar composite has been recognized as an effective way to enhance the removal of pollutants. The interaction between clay mineral and biomass during thermal pyrolysis and the sorption capacity for ionic/nonionic organic containments have not been elaborated. In this study, two types of biochar were obtained from pyrolytic carbonization of the cellulosic-rich corn straw (C) and lignin-rich pine wood (P) at 500 or 700 °C. Typical clay minerals kaolinite and montmorillonite were selected to prepare clay-biochar composite. The results showed that the addition of clay mineral could strengthen dehydration reaction of corn straw biomass and reinforce its carbon structure. Montmorillonite-biochar composite owned more CC functional groups and porous structure than kaolinite-biochar composite. The addition of clay minerals could promote electrostatic attraction of ionic formed norfloxacin (NOR) on clay-pine wood biochar. However, the sorption capacity of nonionic diethyl phthalate (DEP) adsorption on clay-corn straw biochar decreased, owing to that clay increased the compactness of the biochar carbon structure, thus inhabited hydrophobic partition of nonionic organic compounds on disordered carbon fraction. The results from this study provide insights into the suitable contaminated site remediation by clay-biochar composite.

Digestion of plastics using in vitro human gastrointestinal tract and their potential to adsorb emerging organic pollutants

Excessive plastic use has inevitably led to its consumption by organisms, including humans. It is estimated that humans consume 20 kg of plastic during their lifetime. The presence of microplastics in the human body can carry serious health risks, such as biological reactions e.g. inflammation, genotoxicity, oxidative stress, apoptosis, as well toxic compounds leaching of unbound chemicals/monomers, free radicals or adsorbed organic pollutants, which mainly depend on the properties of the ingested plastic. Plastics are exposed to different substances (e.g., enzymes and acids) in the digestive system, which potentially affects their properties and structure. By stimulating the human digestive system and applying a set of advanced analytical tools, we showed that the surface of polystyrene and high-density polyethylene plastics frequently in contact with food undergoes fundamental changes during digestion. This results in the appearance of additional functional groups, and consequent increase in the plastic adsorption capacity for hydrophobic ionic compounds (such as triclosan and diclofenac) while reducing its adsorption capacity for hydrophobic non-ionic compounds (such as phenanthrene). Micro- and nanostructures that formed on the flat surface of the plastics after digestion were identified using scanning electron microscopy. These structures became defragmented and detached due to mechanical action, increasing micro- and nanoplastics in the environment. Due to their size, the release of plastic nanostructures after digestion can become an “accidental food source” for a wider group of aquatic organisms and ultimately for humans as the last link in the food chain. This, combined with improved adsorption capacity of digested plastics to hydrophobic ionic pollutants, can pose a serious threat to the environment including human health and safety.

Impact of water activity on the radial growth of fungi in a dairy environment

Filamentous fungi are used in the dairy industry as adjunct cultures in fermented products, but can also lead to food spoilage, waste and economic losses. The control of filamentous fungi with abiotic factors contributes to longer food shelf life and prevention of fungal spoilage. One of the main abiotic factors for controlling fungal growth in foods is water activity (aw). This study aimed to evaluate radial growth as a function of aw for sixteen fungal adjuncts and/or spoilers isolated from dairy products or a dairy environment. Glycerol (a non-ionic compound) and sodium chloride (NaCl, an ionic compound) were used to adjust the aw of culture media. This study showed significant diversity in the responses of the tested fungal strains as a function of medium aw. The growth response of Penicillium bialowiezense and Sporendonema casei was binary, with no clear decrease of growth rate until the growth limit, when the aw was reduced. For the strains of Bisifusarium domesticum, Mucor circinelloides and Penicillium camemberti, a decrease of aw had the same impact on radial growth rate regardless of the aw belonging to their growth range. For the strains of Aspergillus flavus, Cladosporium herbarum, Geotrichum candidum, Mucor lanceolatus, Penicillium expansum, Penicillium fuscoglaucum, Penicillium nalgiovense, Paecilomyces niveus, Penicillium roqueforti, Penicillium solitum and Scopulariopsis asperula, the impact of a decrease in aw was more pronounced at high aw than at low aw. A mathematical model was suggested to describe this impact on the radial growth rate. For all tested species, radial growth was more sensitive to NaCl than glycerol. The ionic strength of NaCl mainly explains the difference in the effects of the two solutes.

Benzimidazole-based ionic and non-ionic organoselenium compounds: innovative synthetic strategies, structural characterization and preliminary anti-proliferative activities

Rational design of and efficient synthesis of innovative benzimidazole-based ionic and non-ionic organoselenium compounds is described. The compounds were studied for their anti-proliferative activities against triple-negative breast cancer cells.

Ion Complexation Explains Orders of Magnitude Changes in the Equilibrium Constant of Biochemical Reactions in Buffers Crowded by Nonionic Compounds

The equilibrium constant (K) of biochemical complex formation in aqueous buffers with high concentration (>20 wt %) of nonionic compounds can vary by orders of magnitude in comparison with the K in a pure buffer. The precise molecular mechanisms of these profound changes are not known. Herein, we show up to a 1000-fold decrease of the K value of DNA hybridization (at nM concentration) in standard molecular crowder systems such as PEG, dextrans, Ficoll, and glycerol. The effect responsible for the decrease of K is the complexation of positively charged ions from a buffer by nonionic polymers/small molecules. We determined the average equilibrium constant for the complexation of ions per monomer (∼0.49 M–1). We retrieve K’s original value for a pure buffer if we properly increase the ionic strength of the buffer crowded by the polymers, compensating for the loss of complexed ions.

Probing the Hydrogen Bonded Networks and Ion Interactions in Various Classes of Deep Eutectic Solvents (DESs)

Deep eutectic solvents (DESs) are best defined as mixtures of ionic and non-ionic solid compounds with melting points much lower than the pure compounds. They are comprised of a hydrogen bond donor (HBD) - which is generally the organic salt - and a hydrogen bond acceptor (HBA). They are similar to ionic liquids in turns of their physiochemical properties but are cheaper and easier to make. One of their main tuning parameters is the hydrogen-bonded network since it affects their resulting physiochemical properties. In an effort to characterize the hydrogen-bonded network of various classes of DESs we used multi-(1H, 2H, 13C and 17O) Nuclear Magnetic Resonance (NMR) relaxometry and diffusometry techniques as functions of temperature, frequency and pressure. We studied the ion-ion, ion-solvent and solvent-solvent interactions by focusing on the incorporated dilute probe solute molecules which includes isotopically enriched (13C and 17O) and deuterated (2H) benzene, toluene and carbon dioxide. These measurements were compliment by density, viscosity and ionic conductivity, thereby providing more insight into the effect of intermolecular interactions on the resulting dynamics.Results show that in spite of their high viscosities, the ionic conductivity values (see Fig. 1a) for the DESs were comparable to those obtained for selected ionic liquids comprised of the common 1-alkyl-3-methylimidazolium (CnMIM+) cation and bis(trifluoromethylsulfonyl)amide, bis(pentafluoroethylysulfonyl)amide or bis(fluorosulfonyl)amide anion, which are considered as some of the most conductive. Additionally, their Walden Product (see Fig. 1b) shows their classification as ‘subionic’, suggesting there is either significant cation-anion pairing, or their respective motions are correlated. These results and more will be discussed in detail during our presentation. Figure 1. (a) Variable temperature ionic conductivity data and (b)Walden Productsfor selected DESs. Figure 1

A New Strategy for the Preparation of E Isomers of Hydrazones and Anil‐Like Compounds: Thermally Stimulated Isomerization of Z Isomers of Anions

AbstractA new, simple method for the preparation of E‐isomers of hydrazones and anil‐like compounds from Z‐isomers of these compounds has been developed. In DMF, the Z‐isomers of these compounds in the presence of tetrabutylammonium fluoride (TBAF) or tetrabutylammonium acetate (TBAA) gave the corresponding N anions of the Z‐isomers, which are isomerized to the N anions of the E‐isomers even at room temperature. Upon addition of a protic solvent (H2O, or CH3OH) to this reaction mixture, the N anion of the E‐isomer was immediately quantitatively converted to the E‐isomer of the corresponding nonionic compound, which can be readily isolated by methods commonly used in the synthesis.

Emerging Designs of Aggregation-Induced Emission Agents for Enhanced Phototherapy Applications

Emerging Designs of Aggregation-Induced Emission Agents for Enhanced Phototherapy Applications

Magnetically Manipulable Ionic Liquid Crystals Incorporating Neutral Radical Moiety.

With a view to fabricating a new remote input-output system by applying functional ionic liquid crystalline (ILC) materials, we have developed novel ILC compounds containing a nitroxide radical unit in the organic cations, which show an enantiotropic smectic A (SmA) phase. We have implemented the magnetic manipulation of a droplet of one of the ILC compounds on the basis of the intermolecular magnetic interactions between radical moieties. This ILC monoradical compound shows a 55 % larger increase in paramagnetic susceptibility at the solid-to-LC melting point in the first heating process than the non-ionic LC monoradical compounds. It is most likely owing to the nanosegregation of strongly bonded ionic and non-ionic moieties. The increased molar magnetic susceptibility is preserved not only in the SmA phase but also in the isotropic liquid and solid phases during the first cooling process.

Niosomes formation using a continuous supercritical CO2 assisted process

The production of biocompatible nanocarriers, to induce a controlled, sustained and/or targeted drug delivery, is a fascinating nanotechnology challenge. Among the possible nanocarriers, niosomes are non-ionic compounds, with a lipophilic tail and a hydrophilic head, that can self-assemble in aqueous dispersions and can show a good stability over time. In this work, a continuous process, assisted by supercritical CO2, was used for the production of empty and theophylline loaded niosomes. The optimal results, in terms of niosomes nanometric dimension and stability verified up to 30 days, were obtained processing an ethanolic solution at a 90/10 Span® 80 to Tween® 80 ratio. A drug encapsulation efficiency of 85 % was measured when the supercritical process was carried out using a water flow rate of 1 mL/min. Theophylline release time was prolonged up to 5-folds, when this active compound was loaded in niosomes prepared at the largest surfactant to water ratio (100 mg/g).