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The stability of soil organic matter (SOM) is crucial for metal transport and carbon cycling. S,S-ethylenediaminedisuccinic acid (EDDS) is widely used to enhance phytoremediation efficiency for heavy metals in contaminated soils, yet its specific impacts on SOM have been underexplored. This study investigates the effects of EDDS on SOM stability using a rhizobox experiment with ryegrass. Changes in soil dissolved organic matter (DOM) quantity and molecular composition were analyzed via Fourier transform ion cyclotron resonance mass spectrometry. Results showed that the use of EDDS increased the uptake of Cu, Cd and Pb by ryegrass, but simultaneously induced the destabilization and transformation of SOM. After 7 days of EDDS application, dissolved organic carbon (DOC) and nitrogen (DON) concentrations in rhizosphere soils increased significantly by 3.44 and 10.2 times, respectively. In addition, EDDS reduced lipids (56.3%) and proteins/amino sugars-like compounds (52.1%), while increasing tannins (9.11%) and condensed aromatics-like compounds (24.4%) in the rhizosphere DOM. These effects likely stem from EDDS's dual action: extracting Fe/Al from SOM-mineral aggregates, releasing SOM into the DOM pool, and promoting microbial degradation of bioavailable carbon through chain scission and dehydration. Our study firstly revealed that the application of EDDS in phytoremediation increased the mineralization of SOM and release of CO 2 from soil to the atmosphere, which is important to assess the carbon budget of phytoremediation and develop climate-smart strategy in future., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

In this work, multiple extraction thermal desorption (METD), as a sample introduction method for GC, was developed. This technique was used for the determination of residual solvents (RS) in modified cellulose, because it is practically impossible to dissolve or distribute it uniformly in water and common organic solvents. Moreover, METD facilitates the optimization of the desorption time and it is more sensitive to quantify trace level volatiles in insoluble material, compared to direct dynamic desorption (DDD). In addition, METD provides diagnostic information about the sample-sorbent interaction. Three solvents (methanol, ethanol and tert-butanol) were determined in two types of modified cellulose (dialdehyde cellulose (DAC) and DAC-ethylenediamine (DAC-EDA)). It was shown that good linearity over a wide concentration range was achieved. The limits of detection (LOD) and limits of quantification (LOQ) for the different solvents ranged from 0.1 to 0.3 μg and from 0.3 to 0.9 μg per tube, respectively. Accuracy of the METD method was verified by using an alternative method based on the decomposition of the modified celluloses by Trichoderma reesei cellulase, followed by headspace-trap-GC (HS-trap-GC). The results obtained from the two validated methods were found to be similar (relative deviation < 17.0 %). However, the developed METD-GC method is preferable for the analysis of RS in modified cellulose since it does not require sample pretreatment and possesses higher sensitivity., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The study develops polyamine-functionalized graphene oxide-supported NiCo 2 S 4 nanomaterial using a metal-organic framework (MOF). This modification adds free amines and oxygen functionality to the graphene oxide electrode surface, resulting in the decrease in the 2 theta value from 11.2 to 7.1 and an increase in the interlayer spacing value from 1.4 to 7.8 nm. This modification enhances the surface properties, leading to improved wettability and dispersion stability. Additionally, bimetallic nanoparticles of NiCo 2 S 4 , synthesized via the ZIF-67 MOF template, further enhance performance. Analysis confirms the successful fabrication of ZIF-67/f-GO/NiCo 2 S 4 electrode material through various techniques such as XPS spectra, FE-SEM, XRD, and Raman spectra. The resulting Salen-fGO@NiCo 2 S 4 composite exhibits impressive specific capacitance, reaching 2581.65 F g -1 at 10 A g -1 with 82% capacity retention after 5000 cycles. Employing this composite in a hybrid supercapacitor yields remarkable energy and power densities of 40 and 920 W kg -1 , individually, while maintaining 74% capacity retention rate at 10 A g -1 . These findings offer promising prospects for advanced energy storage applications., (© 2024 John Wiley & Sons Ltd.)

A comparative study of the copolymerization of racemic propylene oxide (PO) with CO 2 catalyzed by racemic (salcy)CoX (salcy = N , N '-bis(3,5-di- tert -butylsalicylidene)-1,2-diaminocyclohexane; X = perfluorobenzoate (OBzF 5 ) or 2,4-dinitrophenoxy (DNP)) in the presence of a [PPN]Cl ([PPN] = bis(triphenylphosphine)iminium) cocatalyst is performed in bulk at 21 °C and a 2.5 MPa pressure of CO 2 . The increase in the nucleophilicity of an attacking anion results in the increase in the copolymerization rate. Racemic (salcy)CoX provides a high selectivity of the copolymerization, which can be higher than 99%, and the living polymerization mechanism. Poly(propylene carbonate) (PPC) with bimodal molecular weight distribution (MWD) is formed throughout copolymerization. Both modes are living and are characterized by low dispersity, while their contribution to MWD depends on the nature of the attacking anion. The racemic (salcy)CoDNP/[PPN]DNP system is found to be preferable for the production of PPC with a high yield and selectivity.

The need for a systematic approach in developing new metal-based drugs with dual anticancer-antimicrobial properties is emphasized by the vulnerability of cancer patients to bacterial infections. In this context, a novel organometallic assembly was designed, featuring ruthenium(II) coordination with p-cymene, one chlorido ligand, and a bidentate neutral Schiff base derived from 4-methoxybenzaldehyde and N,N-dimethylethylenediamine. The compound was extensively characterized in both solid-state and solution, employing single crystal X-ray diffraction, nuclear magnetic resonance, infrared, ultraviolet-visible spectroscopy, and density functional theory, alongside Hirshfeld surface analysis. The hydrolysis kinetic was thoroughly investigated, revealing the important role of the chloro-aqua equilibrium in the dynamics of binding with deoxyribonucleic acid and bovine serum albumin. Notably, the aqua species exhibited a pronounced affinity for deoxyribonucleic acid, engaging through electrostatic and hydrogen bonding interactions, while the chloro species demonstrated groove-binding properties. Interaction with albumin revealed distinct binding mechanisms. The aqua species displayed covalent binding, contrasting with the ligand-like van der Waals interactions and hydrogen bonding observed with the chloro specie. Molecular docking studies highlighted site-specific interactions with biomolecular targets. Remarkably, the compound exhibited wide spectrum moderate antimicrobial activity against Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans, coupled with low micromolar cytotoxic activity against human colorectal adenocarcinoma cells and significant activity against human leukemic monocyte lymphoma cells. The presented findings encourage further development of this compound, promising avenues for its evolution into a versatile therapeutic agent targeting both infectious diseases and cancer., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Lead (Pb), a persistent and bio-accumulative contaminant, poses threats to the environment and human health. The effective removal of Pb from contaminated soil proves challenging due to its tendency to form stable complexes with soil components. Chelators have been extensively studied for their ability to extract metal contaminants, including Pb, from soil environment. However, the prolonged environmental persistence of traditional chelators and the high cost of biodegradable alternatives have hindered their practical application in remediation efforts. This study investigated a novel synergistic approach that combined a biodegradable chelator, [S,S]-ethylenediamine succinic acid (EDDS), with cationic and anionic surfactants to enhance Pb extraction efficiency. The study revealed that cationic surfactants, such as cetylpyridinium chloride (CPC) and cetyltrimethylammonium bromide (CTAB), significantly enhanced Pb extraction efficiency when combined with EDDS, whereas anionic surfactants, like sodium N-dodecanoyl-taurinate (SDT) and sodium dodecyl sulfate (SDS), inhibited the extraction process. Specifically, blending 5 mmol L -1 EDDS with 20 mmol L -1 CPC resulted in a 72.6% enhancement in Pb extraction efficiency. The proposed synergistic strategy offers a promising avenue for soil remediation, mitigating Pb contamination while preserving essential soil minerals. By addressing chelator limitations and improving efficiency, this approach presents a viable solution for enhancing soil remediation practices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In this work, a fluorescence chemical sensor continuous detection Al 3+ and phosphates by a Salamo-Salen-Salamo type compound (SL) was employed. The sensor continuously recognized Al 3+ and phosphates with good selectivity and fast response time, and a low limit of detection of 0.25 μΜ and 0.96 μM, at the same time accompanied by a naked-eye identification specificity. The detection mechanism of SL towards Al 3+ is due to the chelating fluorescence enhancement effect and ICT effect, and continuously towards phosphates is due to the collapse of the SL-Al 3+ and coordination interaction between Al 3+ and phosphates, by Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, other spectral characterization and DFT calculation as evidence. In addition, the sensor had good recyclability and reusability. The distribution of Al 3+ and phosphates in zebrafish cells was effectively monitored by confocal microscopy based on the good biocompatibility and tissue permeability of SL. Furthermore, the feasibility of using sensor SL to detect the content of Al 3+ and phosphate ions in certain drugs was quantitatively analyzed through experiments. It was found SL had a good result in practical application., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

Establishing an effective system to measure formaldehyde (HCHO) content in food is of great significance due to food safety concern. Inspired by the mechanism of HCHO-induced protein denaturation and its effect on ion/molecule transport in nanochannels, a bioinspired microchannel-based electrochemiluminescence (ECL) sensor was constructed for HCHO detection. Benefiting from the water solubility of HCHO, the molecules rapidly spread and enriched at the ethylenediamine (EDA) functionalized microchannel interface. The reaction between EDA and HCHO significantly increased the negative charge density, leading to enhanced electroosmotic flow (EOF). This enhancement resulted in ion concentration depletion at the microchannel tip and a corresponding decrease in ionic current and ECL intensity. The ECL intensity exhibited a linear dependence on the logarithm of HCHO concentration ranging from 1 pg mL -1 to 100 ng mL -1 , with a detection limit of 0.26 pg mL -1 (S/N = 3). The biosensor demonstrated high selectivity, successfully detecting HCHO in shrimp samples. The performance of the bioinspired sensor was confirmed through comparation with existing methods, showcasing its superior sensitivity and reliability. The bioinspired sensor provides robust technical support for HCHO detection, crucial for food safety monitoring. Additionally, the innovative combination of bionics and microchannel-based ECL technology broadens the application range of ECL sensors, marking a significant advancement in the field., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The separation of enantiomers using chiral membranes has garnered much research interest. In this study, the enantioseparation of amino acids using chiral membranes, namely graphene oxide-ethylenediamine-maltodextrin (GO-EDA-MD) and GO-EDA-hydroxypropyl-MD (GO-EDA-HP-MD), was evaluated. HP-MD and MD were investigated as chiral selectors due to their inherent chirality. Various characterization techniques, including atomic force microscopy, Fourier transform infrared spectrometry, field emission scanning electron microscopy, water contact angle analysis, tensile properties, and thermal gravimetric analysis were employed to analyze the membrane structures. The evaluation of enantioseparation performance was conducted by employing tryptophan, phenylalanine, and tyrosine enantiomers. Optimal conditions for enantiomer separation were achived using a GO-EDA-HP-MD chiral composite (1.75 wt%), a feed concentration of 10 mg/L for each enantiomer, a separation time of 15 min, and a membrane effective surface area of 1.0 cm 2 . Also, the bovine serum albumin rejection was 90.0 %, and the water flux reached 37.1 L m -2 h -1 . The highest enantiomeric excess (ee.%) values were 46.33 %, 76.97 %, and 73.04 % for tryptophan, phenylalanine, and tyrosine, respectively. The impact of voltage on ee.% and substance flux was also explored. This membrane was able to separate enantiomers successfully., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

The present study aims to obtain manganese ferrite nanoparticles functionalized with chitosan (C-MNP) or ethylenediamine (E-MNP) by coprecipitation and polyol one-step methods, characterize their interaction with S. griseus demonstrating cell immobilization, and evaluate the antimicrobial activity of the free cell extracts obtained from immobilized S. griseus fermentation in the presence of different concentrations of MNP. The adsorption isotherms were analyzed mathematically using Langmuir and Freundlich models. The highest coefficient of determination (R 2 ) for the S. griseus cell adsorption isotherm with C-MNP was observed with a linear function of the Langmuir model. The adsorption isotherm of S. griseus cells with E-MNP was better fitted to the Freundlich model. Cell immobilization by adsorption on magnetic nanoparticles was demonstrated in both cases. Different concentrations of C-MNP and E-MNP were used in fermentations to prepare cell-free extracts with antifungal activity. The best results were obtained with E-MNP, with a 91.5% inhibition of radial fungal growth. Magnetic nanoparticles offer potential applications in different fields and easy biomass separation., Competing Interests: Declarations. Ethical Approval: It is an observational study. The Universidad Autonoma de Coahuila Ethics Committee has confirmed that no ethical approval is required to develop the present study. Consent to Participate: Informed consent was not strictly required to develop the present research, as neither humans nor animals were involved. Consent for Publication: Consent to publish was unnecessary for developing the present research work as neither humans nor animals were involved. Competing Interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature.)

Iron(III) complexes based on N,N´-bis(salicylidene)ethylenediamine (salene) scaffolds have demonstrated promising anticancer features like induction of ferroptosis, an iron dependent cell death. Since poor cellular uptake limits their therapeutical potential, this study aimed to enhance the lipophilic character of chlorido[N,N'-bis(salicylidene)-1,2-bis(3-methoxyphenyl)ethylenediamine]iron(III) complexes by introducing lipophilicity improving ligands such as fluorine (X1), chlorine (X2) and bromine (X3) in 5-position in the salicylidene moieties. After detailed characterization the binding to nucleophiles, logP values and cellular uptake were determined. The complexes were further evaluated regarding their biological activity on MDA-MB 231 mammary carcinoma, the non-tumorous SV-80 fibroblast, HS-5 stroma and MCF-10A mammary gland cell lines. Stability of the complexes in aqueous and biological environments was proven by the lack of interactions with amino acids and glutathione. Cellular uptake was positively correlated with the logP values, indicating that higher lipophilicity enhanced cellular uptake. The complexes induced strong antiproliferative and antimetabolic effects on MDA-MB 231 cells, but were inactive on all non-malignant cells tested. Generation of mitochondrial reactive oxygen species, increase of lipid peroxidation and induction of both ferroptosis and necroptosis were identified as mechanisms of action. In conclusion, halogenation of chlorido[N,N'-bis(salicylidene)-1,2-bis(3-methoxyphenyl)ethylenediamine]iron(III) complexes raises their lipophilic character resulting in improved cellular uptake., (© 2024. The Author(s).)

The cytochrome P450 is a superfamily of hemoproteins mainly present in the liver and are versatile biocatalysts. They participate in the primary metabolism and biosynthesis of various secondary metabolites. Chemical catalysts are utilized to replicate the activities of enzymes. Metalloporphyrins and Salen complexes can contribute to the products' characterization and elucidate biotransformation processes, which are investigated during pre-clinical trials. These catalysts also help discover biologically active compounds and get better yields of products of industrial interest. This review aims to investigate which natural product classes are being investigated by biomimetic chemical models and the functionalities applied in the use of these catalysts. A limited number of studies were observed, with terpenes and alkaloids being the most investigated natural product classes. The research also revealed that Metalloporphyrins are still the most popular in the studies, and the identity and yield of the products obtained depend on the reaction system conditions., (© 2024 Wiley-VHCA AG, Zurich, Switzerland.)

Extensive research has been conducted on the utilization of a metal-based catalyst to activate peracetic acid (PAA) for the degradation of micropollutants (MPs) in water. Mn(II) is a commonly employed catalyst for homogeneous advanced oxidation processes (AOPs), but its catalytic performance with PAA is poor. This study showed that the environmentally friendly chelator ethylenediamine- N , N '-disuccinic acid (EDDS) could greatly facilitate the activation of Mn(II) in PAA for complete atrazine (ATZ) degradation. In this process, the EDDS enhanced the catalytic activity of manganese (Mn) and prevented disproportionation of transient Mn species, thus facilitating the decay of PAA and mineralization of ATZ. By employing electron spin resonance detection, quenching and probe tests, and 18 O isotope-tracing experiments, the significance of high-valent Mn-oxo species (Mn(V)) in the Mn(II)-EDDS/PAA system was revealed. In particular, the involvement of the Mn(III) species was essential for the formation of Mn(V). Mn(III) species, along with singlet oxygen ( 1 O 2 ) and acetyl(per)oxyl radicals (CH 3 C(O)O • /CH 3 C(O)OO • ), also contributed partially to ATZ degradation. Mass spectrometry and density functional theory methods were used to study the transformation pathway and mechanism of ATZ. The toxicity assessment of the oxidative products indicated that the toxicity of ATZ decreased after the degradation reaction. Moreover, the system exhibited excellent interference resistance toward various anions and humid acid (HA), and it could selectively degrade multiple MPs.

Ru-based electrochemiluminescence (ECL) coordination polymers are widely employed for bioanalysis and medical diagnosis. However, commonly used Ru-based coordination polymers face the limitation of low efficiency due to the long distance between the ECL reagent and the coreactant dispersed in detecting solution. Herein, we report a dual-ligand self-enhanced ECL coordination polymer, composed of tris(4,4'-dicarboxylic acid-2,2'-bipyridyl) ruthenium(II) dichloride (Ru(dcbpy) 3 2+ ) as ECL reactant ligand and ethylenediamine (EDA) as corresponding coreactant ligand into Zn 2+ metal node, termed Zn-Ru-EDA. Zn-Ru-EDA shows excellent ECL performance which is attributed to the effective intramolecular electron transport between the two ligands. Furthermore, the dual-ligand polymer allows an anodic low excitation potential (+1.09 V) luminescence. The shift in the energy level of the highest occupied molecular orbital (HOMO) upward after the synthesis of the Zn-Ru-EDA has resulted in a reduced excitation potential. The low excitation potential reduced biomolecular damage and the destruction of the modified electrodes. The ECL biosensor has been constructed using Zn-Ru-EDA with high ECL efficiency for the ultrasensitive detection of a bacterial infection and sepsis biomarker, procalcitonin (PCT), in the range from 1.00 × 10 -6 to 1.00 × 10 ng·mL -1 with outstanding selectivity, and the detection limit was as low as 0.47 fg·mL -1 . Collectively, the dual-ligand-based self-enhanced polymer may provide an ideal strategy for high ECL efficiency improvement as well as designing new self-enhanced multiple-ligand-based coordination in sensitive biomolecular detection for early disease diagnostics.

Redox-conducting polymers based on SalEn-type complexes have attracted considerable attention due to their potential applications in electrochemical devices. However, their charge transfer mechanisms, physical and electrochemical properties remain unclear, hindering their rational design and optimization. This study aims to establish the influence of monomer geometry on the polymer's properties by investigating the properties of novel nonplanar SalEn-type complexes, poly[N,N'-bis(salicylidene)propylene-2-(hydroxy)diaminonickel(II)], and its analog with 2,2,6,6-tetramethylpiperidinyl-N-oxyl (TEMPO)-substituted bridge (MTS). To elucidate the charge transfer mechanism, operando UV-Vis spectroelectrochemical analysis, electrochemical impedance spectroscopy, and electron paramagnetic resonance are employed. Introducing TEMPO into the bridge moiety enhanced the specific capacity of the poly(MTS) material to 95 mA h g -1 , attributed to TEMPO's and conductive backbone's charge storage capabilities. Replacement of the ethylenediimino-bridge with a 1,3-propylenediimino- bridge induced significant changes in the complex geometry and material's morphology, electrochemical, and spectral properties. At nearly the same potential, polaron and bipolaron particles emerged, suggesting intriguing features at the overlap point of the electroactivity potentials ranges of polaron-bipolaron and TEMPO, such as a disruption in the connection between TEMPO and the conjugation chain or intramolecular charge transfer. These results offer valuable insights for optimizing strategies to create organic materials with tailored properties for use in catalysis and battery applications., (© 2024 Wiley‐VCH GmbH.)

Cell senescence is defined as irreversible cell cycle arrest, which can be triggered by telomere shortening or by various types of genotoxic stress. Induction of senescence is emerging as a new strategy for the treatment of cancer, especially when sequentially combined with a second senolytic drug capable of killing the resulting senescent cells, however severely suffering from the undesired off-target side effects from the senolytic drugs. Here, we prepare a bimetalic platinum-aluminum salen complex (Alumiplatin) for cancer therapy-a combination of pro-senesence chemotherapy with in situ senotherapy to avoid the side effects. The aluminum salen moiety, as a G-quadruplex stabilizer, enhances the salen's ability to induce cancer cell senescence and this phenotype is in turn sensitive to the cytotoxic activity of the monofunctional platinum moiety. It exhibits an excellent capability for inducing senescence, a potent cytotoxic activity against cancer cells both in vitro and in vivo, and an improved safety profile compared to cisplatin. Therefore, Alumiplatin may be a good candidate to be further developed into safe and effective anticancer agents. This novel combination of cell senescence inducers with genotoxic drugs revolutionizes the therapy options of designing multi-targeting anticancer agents to improve the efficacy of anticancer therapies., (© 2024 Wiley-VCH GmbH.)

β-lactoglobulin (BLG) is the major whey protein with negative charges at neutral pH in aqueous media. Thus, the interaction with mucins, the major polyanionic component of mucus, is very weak due to the electrostatic repulsion between them. The present study postulates that cationization of BLG molecules may reverse the interaction characteristics between BLG and mucin from repulsive to associative. To this end, cationic-modified BLGs were prepared by grafting positively charged ethylenediamine (EDA) moieties into the negatively charged carboxyl groups on the aspartic and glutamic acid residues and compared with non-modified BLG upon mixing with porcine gastric mucin (PGM). To characterize the structural and conformational features of PGM, non/cationized BLGs, and their mixtures, various spectroscopic approaches, including zeta potential, dynamic light scattering (DLS), and circular dichroism (CD) spectroscopy were employed. Importantly, we have taken surface adsorption with optical waveguide lightmode spectroscopy (OWLS), and tribological properties with pin-on-disk tribometry at the sliding interface as the key approaches to determine the interaction nature between them as mixing PGM with polycations can lead to synergistic lubrication at the nonpolar substrate in neutral aqueous media as a result of an electrostatic association. All the spectroscopic studies and a substantial improvement in lubricity collectively supported a tenacious and associative interaction between PGM and cationized BLGs, but not between PGM and non-modified BLG. This study demonstrates a unique and successful approach to intensify the interaction between BLG and mucins, which is meaningful for a broad range of disciplines, including food science, macromolecular interactions, and biolubrication etc., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

In the pharmaceutical industry, effective risk management and control strategies for potential genotoxic impurities are of paramount importance. The current study utilized GC-MS to evaluate a precise, linear, and accurate analytical method for quantifying ethylenediamine present in tripelennamine hydrochloride using phthalaldehyde as a derivatizing agent. When phthalaldehyde is sonicated for 10 min at room temperature, it reacts with ethylenediamine to form (1z,5z)-3,4-dihydrobenzo[f][1,4]diazocine. This approach minimizes matrix interference issues and resolves sample preparation difficulties encountered during ethylenediamine identification in GC-MS. In this method, helium serves as the carrier gas, while methanol acts as the diluent. The stationary phase consists of a DB-5MS column (30 m × 0.25 mm × 0.25 μm) with a flow rate of 1.5 mL/min. The retention time of (1z,5z)-3,4-dihydrobenzo[f][1,4]diazocine was determined to be 6.215 min. The method validation demonstrated limits of detection and quantification for (1z,5z)-3,4-dihydrobenzo[f][1,4]diazocine at 0.4 and 1.0 ppm, respectively, with a linearity range spanning from 1 to 30 ppm concentration with respect to the specification level. System suitability, precision, linearity, and accuracy of the current method were assessed in accordance with guidelines, yielding results deemed suitable for the intended use., (© 2024 John Wiley & Sons Ltd.)

Drugs that are poorly soluble in water are difficult to absorb orally, resulting in low bioavailability. Flurbiprofen (FLU) is an arylpropionic acid nonsteroidal anti-inflammatory drug belonging to BCS class II, with low water solubility. In this study, a novel flurbiprofen-ethylenediamine salt (FLU-EDA) was successfully prepared via solvent crystallization. Its crystal structure was determined via single-crystal X-ray diffraction (SXRD). Further, the physicochemical properties of FLU-EDA salt were characterized by powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and Fourier transform infrared spectroscopy (FT-IR). The solubility and intrinsic dissolution rate (IDR) of FLU-EDA salt in water were investigated. The results showed that compared with FLU, the solubility and IDR of FLU-EDA salt increased by 57-fold and 32-fold, respectively. This indicates that FLU-EDA salt can significantly enhance the solubility and dissolution rate of flurbiprofen in water. This study provides basic data and theory for the development of new formulations of flurbiprofen., (© 2023 The Authors. ChemistryOpen published by Wiley-VCH GmbH.)

Organic-inorganic hybrid materials have emerged as a class of novel materials over the last two decades, as they combine functional organic components and inorganic building blocks into unique materials through various chemical or physical interactions. In the present work, the importance of the use of ethylenediamine in sulfided materials applied to photocatalytic processes in the H 2 production is demonstrated. The ZnS/ZnO heterojunction was prepared by the solvothermal synthesis in the presence and absence of ethylenediamine. The photocatalytic behavior showed that the addition of ethylenediamine increases the photocatalytic efficiency up to eight times compared to the photocatalyst without the organic agent. The materials were characterized by X-ray diffraction, scanning electron microscopy, infrared and UV-visible spectroscopies of solids, N 2 adsorption-desorption isotherms, X-ray photoelectron spectroscopy, and photoelectrochemical characterization. The ethylenediamine plays a double role: to stabilize the cubic phase of zinc sulfide and to act as a promoter molecule of charge transfer on the surface of ZnS/ZnO/en heterojunction, slowing down the rate of recombination of the electron-hole pair, which is reflected in a decrease in the resistance to transfer of charge carriers, improving the H 2 production rate until 1564 µmol h -1  g -1 ., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The impact of methoxy and hydroxyl groups at the salicylidene moiety of chlorido[ N , N '-bis(methoxy/hydroxy)salicylidene-1,2-bis(4-methoxyphenyl)ethylenediamine]iron(III) complexes was evaluated on human MDA-MB 231 breast cancer and HL-60 leukemia cells. Methoxylated complexes ( C1 - C3 ) inhibited proliferation, migration, and metabolic activity in a concentration-dependent manner following the rank order: C2 > C3 > C1 . In particular, C2 was highly cytotoxic with an IC 50 of 4.2 μM which was 6.6-fold lower than that of cisplatin (IC 50 of 27.9 μM). In contrast, hydroxylated complexes C4 - C6 were almost inactive up to the highest concentration tested due to lack of cellular uptake. C2 caused a dual mode of cell death, ferroptosis, and necroptosis, whereby at higher concentrations, ferroptosis was the preferred form. Ferroptotic morphology and the presence of ferrous iron and lipid reactive oxygen species proved the involvement of ferroptosis. C2 was identified as a promising lead compound for the design of drug candidates inducing ferroptosis.

Chemically assisted phytoremediation is suggested as an effective approach to amplify the metal-remediating potential of hyperaccumulators. The current study assessed the efficiency of two biodegradable chelants (S,S-ethylenediamine disuccinic acid, EDDS; nitrilotriacetic acid, NTA) in enhancing the remediation of Cd by Coronopus didymus (Brassicaceae). C. didymus growing in Cd-contaminated soil (35-175 mg kg -1 soil) showed increased growth and biomass due to the hormesis effect, and chelant supplementation further increased growth, biomass, and Cd accumulation. A significant interaction with chelants and different Cd concentrations was observed, except for Cd content in roots and Cd content in leaves, which exhibited a non-significant interaction with chelant addition. The effect of the NTA amendment on the root dry biomass and shoot dry biomass was more pronounced than EDDS at all the Cd treatments. Upon addition of EDDS and NTA, bio-concentration factor values were enhanced by ~184-205 and ~ 199-208, respectively. The tolerance index of root and shoot increased over the control upon the addition of chelants, with NTA being better than EDDS. With chelant supplementation, bio-accumulation coefficient values were in the order Cd 35  + NTA (~163%) > Cd 105  + NTA (~137%) > Cd 35  + EDDS (~89%) > Cd 175  + NTA (~85%) > Cd 105  + EDDS (~62%) > Cd 175  + EDDS (~40%). The translocation factor correlated positively (r ≥ 0.8) with tolerance index and Cd accumulation in different plant parts. The study demonstrated that chelant supplementation enhanced Cd-remediation efficiency in C. didymus as depicted by improved plant growth and metal accumulation, and NTA was more effective than EDDS in reclaiming Cd., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

A comparative study of the electronic structure of the salen ligand in the H 2 (Salen) molecule and the [Ni(Salen)] complex was performed using the experimental methods of XPS, UV PES, and NEXAFS spectroscopy along with DFT calculations. Significant chemical shifts of +1.0 eV (carbon), +1.9 eV (nitrogen), and -0.4 eV (oxygen) were observed in the 1s PE spectra of the salen ligand atoms when passing from a molecule to a complex, unambiguously indicating a substantial redistribution of the valence electron density between these atoms. It is proposed that the electron density transfer to the O atoms in [Ni(Salen)] occurred not only from the Ni atom, but also from the N and C atoms. This process seemed to be realized through the delocalized conjugated π-system of the phenol C 2p electronic states of the ligand molecule. The DFT calculations (total and partial DOS) for the valence band H 2 (Salen) and [Ni(Salen)] described well the spectral shape of the UV PE spectra of both compounds and confirmed their experimental identification. An analysis of the N and O 1s NEXAFS spectra clearly indicated that the atomic structure of the ethylenediamine and phenol fragments was retained upon passing from the free salen ligand to the nickel complex.

The linking of ethacrynic acid with ethylenediamine and 1,4-butanediamine gave EDEA and BDEA, respectively, as membrane-permeable divalent pro-inhibitors of glutathione S -transferase (GST). Their divalent glutathione conjugates showed subnanomolar inhibition and divalence-binding to GSTmu (GSTM) (PDB: 5HWL) at ∼0.35 min -1 . In cisplatin-resistant SK-OV-3, COC1, SGC7901 and A549 cells, GSTM activities probed by 15 nM BDEA or EDEA revealed 5-fold and 1.0-fold increases in cisplatin-resistant SK-OV-3 and COC1 cells, respectively, in comparison with the susceptible parental cells. Being tolerable by HEK293 and LO2 cells, BDEA at 0.2 μM sensitised resistant SK-OV-3 and COC1 cells by ∼3- and ∼5-folds, respectively, released cytochrome c and increased apoptosis; EDEA at 1.0 μM sensitised resistant SK-OV-3 and A549 cells by ∼5- and ∼7-fold, respectively. EDEA at 1.7 μg/g sensitised resistant SK-OV-3 cells to cisplatin at 3.3 μg/g in nude mouse xenograft model. BDEA and EDEA are promising leads for probing cellular GSTM and sensitising cisplatin-resistant ovarian cancers.

Moderate Zn 2+ selectivity over Cd 2+ ( I Zn / I Cd = 1.6) in the fluorescence enhancement of TQEN ( N , N , N ', N '-tetrakis(2-quinolylmethyl)ethylenediamine) was changed to Cd 2+ preference via the introduction of a methoxymethyloxy (MOMO) substituent at the 8-position of one of the four quinoline rings ( I Zn / I Cd = 0.2). Thus, 8-MOMOTQEN ( N -(8-methoxymethyloxy-2-quinolylmethyl)- N , N ', N '-tris(2-quinolylmethyl)ethylenediamine) showed not only high Cd 2+ -selectivity but also an enhanced fluorescence quantum yield upon Cd 2+ binding and high sensitivity for Cd 2+ detection as shown by ϕ Cd = 0.065 and LOD (limit of detection) = 19 nM. The two oxygen atoms of the MOMO group in 8-MOMOTQEN play a crucial role in the fluorescent metal-ion selectivity because the corresponding hydroxy (8-OHTQEN) and methoxy (8-MeOTQEN) derivatives resulted in a poor fluorescent response and metal selectivity, respectively. Another N6O2 ligand, N , N '-bis(8-methoxy-2-quinolylethyl)- N , N '-bis(2-quinolylmethyl)ethylenediamine ((8-MeO) 2 TQEN) exhibited a Zn 2+ -selective fluorescence enhancement ( I Zn / I Cd = 2.2), indicating the superiority of the MOMO group for the selective sensing of Cd 2+ .

The colocalization of taurine and zinc transporters (TAUT, ZnTs) has not been explored in retina. Our objective is to evaluate the effect of the intracellular zinc chelator N,N,N,N-tetrakis-(2-pyridylmethyl) ethylenediamine (TPEN) on zinc localization and colocalization TAUT and ZnT-1 (of plasma membrane), 3 (vesicular), and 7 (vesicular and golgi apparatus) in layers of retina by immunohistochemistry. To mark zinc, it was used cell-permeable fluorescent Zinquin ethyl ester. Specific first and secondary antibodies, conjugated with rhodamine or fluorescein-isothiocyanate were used to mark TAUT and ZnTs. The fluorescence results were reported as integrated optical density (IOD). Zinc was detected in all layers of the retina. The treatment with TPEN produced changes in the distribution of zinc in layers of retina less in the outer nuclear layer compared with the control. TAUT was detected in all layers of retina and TPEN chelator produced decrease of IOD in all layers of retina except in the photoreceptor compared with the control. ZnT 1, 3, and 7 were distributed in all retina layers, with more intensity in ganglion cell layer (GCL) and in the layers where there is synaptic connection. For all transporters, the treatment with TPEN produced significant decrease of IOD in layers of retina least in the inner nuclear layer for ZnT1, in the photoreceptor for ZnT3 and in the GCL and outer plexiform layer for ZnT7. The distribution of zinc, TAUT, and ZnTs in the layers of retina is indicative of the interaction of taurine and zinc for the function of the retina and normal operation of said layers. HIGHLIGHTS: Taurine and zinc are two molecules highly concentrated in the retina and with relevant functions in this structure. Maintaining zinc homeostasis in this tissue is necessary for the normal function of the taurine system in the retina. The study of the taurine transporter and the different zinc transporters in the retina (responsible for maintaining adequate levels of taurine and zinc) is relevant and novel, since it is indicative of the interactions between both molecules in this structure., (© 2022 Wiley Periodicals LLC.)

Toxic contaminants (metals and metal-containing compounds) are accumulating in the environment at an astonishing rate and jeopardize human health. Remarkable industrial revolution and the spectacular economic growth are the prime causes for the release of such toxic contaminants in the environment. Cadmium (Cd) is ranked the 7th most toxic compound by the Agency for Toxic Substances and Disease Registry (USA), owing to its high carcinogenicity and non-biodegradability even at miniscule concentration. The present study assessed the efficiency of four biodegradable chelants [nitrilotriacetic acid (NTA), ethylenediamine disuccinate (EDDS), ethylene glycol tetraacetic acid (EGTA), and citric acid (CA)] and their dose (5 mM and 10 mM) in enhancing metal accumulation in Solanum americanum Mill. (grown under 24 mg Cd kg -1 soil) through morpho-physiological and metal extraction parameters. Significant variations were observed for most of the studied parameters in response to chelants and their doses. However, ratio of root and shoot length, and plant height stress tolerance index differed non-significantly. The potential of chelants to enhance Cd removal efficiency was in the order - EGTA (7.44%) > EDDS (6.05%) > NTA (4.12%) > CA (2.75%). EGTA and EDDS exhibited dose-dependent behavior for Cd extraction with 10 mM dose being more efficient than 5 mM dose. Structural equation model (SEM) depicted strong positive interaction of metal extraction parameters with chelants (Z-value = 11.61, p = 0.001). This study provides insights into the importance of selecting appropriate dose of biodegradable chelants for Cd extraction, as high chelant concentration might also result in phytotoxicity. In the future, phytoextraction potential of these chelants needs to be examined through field studies under natural environmental conditions., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Copolymers are valuable supports for obtaining heterogeneous catalysts that allow their recycling and therefore substantial savings, particularly in the field of asymmetric catalysis. This contribution reports the use of two comonomers: Azido-3-propylmethacrylate (AZMA) bearing a reactive azide function was associated with 2-methoxyethyl methacrylate (MEMA), used as a spacer, for the ATRP synthesis of copolymers, and then post-functionalized with a propargyl chromium salen complex. The controlled homopolymerization of MEMA by ATRP was firstly described and proved to be more controlled in molar mass than that of AZMA for conversions up to 63%. The ATRP copolymerization of both monomers made it possible to control the molar masses and the composition, with nevertheless a slight increase in the dispersity (from 1.05 to 1.3) when the incorporation ratio of AZMA increased from 10 to 50 mol%. These copolymers were post-functionalized with chromium salen units by click chemistry and their activity was evaluated in the asymmetric ring opening of cyclohexene oxide with trimethylsilyl azide. At an equal catalytic ratio, a significant increase in enantioselectivity was obtained by using the copolymer containing the largest part of salen units, probably allowing, in this case, the more favorable bimetallic activation of both the engaged nucleophile and electrophile. Moreover, the catalytic polymer was recovered by simple filtration and re-engaged in subsequent catalytic runs, up to seven times, without loss of activity or selectivity.

Manipulation of a multi-physical quantity to steer a molecular photophysical property is of great significance in improving sensing performance. Here, an investigation on how a physical quantity rooted in the molecular structure induces an optical behavior change to facilitate ultrasensitive detection of ethylenediamine (EDA) is performed by varying a set of thiols. The model molecule consisting of a thiol with dual-carboxyl exhibits the strongest fluorescence, which is ascribed to the electron-donating ability and prompted larger orbital overlap and oscillator strength. The elevated fluorescence positively corelated to the increased EDA, endowing an ultrasensitive response to the nanomolar-liquid/ppm-vapor. A gas detector with superior performance fulfills a contactless and real-time management of EDA. We envisage this electron-tuning strategy-enabled fluorescence enhancement can offer in-depth insight in advancing molecule-customized design, further paving the way to widening applications., (© 2022 Wiley-VCH GmbH.)

Bisimine derivatives of salicylaldehyde with chiral diamines (salens) are privileged ligands in asymmetric organometallic catalysis, which can be used in cooperation with organocatalysts as additives. The latter can be a modifier of the metal reactivity by liganding or a true co-catalyst working in tandem or in a dual system. All scenarios encountered in the literature are reviewed and classified according to the organocatalyst. In each case, mechanistic and physical-organic chemistry considerations are discussed to better understand the gears of these complex catalytic settings.

Aim: To prepare new polycationic pullulan derivatives exhibiting highly mucoadhesive and sustained drug release properties., Methods: Hydroxy groups of pullulan were activated with mesyl chloride followed by conjugation with low-molecular weight polyamines. Pullulan-tris(2-aminoethyl)amine (Pul-TAEA) and pullulan-polyethyleneimine (Pul-PEI) were evaluated regarding swelling behaviour, mucoadhesive properties and potential to control drug release., Results: Pul-TAEA and Pul-PEI exhibited excellent swelling properties at pH 6.8 showing 240- and 370-fold increase in weight. Compared to unmodified pullulan, Pul-TAEA and Pul-PEI displayed 5- and 13.3-fold increased dynamic viscosity in mucus. Mucoadhesion studies of Pul-TAEA and Pul-PEI on intestinal mucosa showed a 6- and 37.8-fold increase in tensile strength, and a 72- and 120-fold increase in mucoadhesion time compared to unmodified pullulan, respectively. Due to additional ionic interactions between cationic groups on polyaminated pullulans and an anionic model drug, a sustained drug release was achieved., Conclusions: Polyaminated pullulans are promising novel mucoadhesive excipients for mucosal drug delivery., (Copyright © 2022. Published by Elsevier Ltd.)

We have synthesized a series of novel substituted sulfonyl ethylenediamine (en) Ru II arene complexes 1-8 of [(η 6 -arene)Ru(R 1 -SO 2 -EnBz)X], where the arene is benzene, HO(CH 2 ) 2 O-phenyl or biphenyl (biph), X = Cl or I, and R 1 is phenyl, 4-Me-phenyl, 4-NO 2 -phenyl or dansyl. The 'piano-stool' structure of complex 3, [(η 6 -biph)Ru(4-Me-phenyl-SO 2 -EnBz)I], was confirmed by X-ray crystallography. The values of their aqua adducts were determined to be high (9.1 to 9.7). Complexes 1-8 have antiproliferative activity against human A2780 ovarian, and A549 lung cancer cells with IC 50 values ranging from 4.1 to >50 μM, although, remarkably, complex 7 [(η 6 -biph)Ru(phenyl-SO 2 -EnBz)Cl] was inactive towards A2780 cells, but as potent as the clinical drug cisplatin towards A549 cells. All these complexes also showed catalytic activity in transfer hydrogenation (TH) of NAD + to NADH with sodium formate as hydride donor, with TOFs in the range of 2.5-9.7 h -1 . The complexes reacted rapidly with the thiols glutathione (GSH) and N -acetyl-L-cysteine (NAC), forming dinuclear bridged complexes [(η 6 -biph) 2 Ru 2 (GS) 3 ] 2- or [(η 6 -biph) 2 Ru 2 (NAC-H) 3 ] 2- , with the liberation of the diamine ligand which was detected by LC-MS. In addition, the switching on of fluorescence for complex 8 in aqueous solution confirmed release of the chelated DsEnBz ligand in reactions with these thiols. Reactions with GSH hampered the catalytic TH of NAD + to NADH due to the decomposition of the complexes. Co-administration to cells of complex 2 [(η 6 -biph)Ru(4-Me-phenyl-SO 2 -EnBz)Cl] with L-buthionine sulfoximine (L-BSO), an inhibitor of GSH synthesis, partially restored the anticancer activity towards A2780 ovarian cancer cells. Complex 2 caused a concentration-dependent G1 phase cell cycle arrest, and induced a significant level of reactive oxygen species (ROS) in A2780 human ovarian cancer cells. The amount of induced ROS decreased with increase in GSH concentration, perhaps due to the formation of the dinuclear Ru-SG complex.

Local electric fields can alter energy landscapes to impart enhanced reactivity in enzymes and at surfaces. Similar fields can be generated in molecular systems using charged functionalities. Manganese(V) salen nitrido complexes (salen = N , N '-ethylenebis(salicylideneaminato)) appended with a crown ether unit containing Na + ( 1-Na ), K + , ( 1-K ), Ba 2+ ( 1-Ba ), Sr 2+ ( 1-Sr ), La 3+ ( 1-La ), or Eu 3+ ( 1-Eu ) cation were investigated to determine the effect of charge on p K a , E 1/2 , and the net bond dissociation free energy (BDFE) of N-H bonds. The series, which includes the manganese(V) salen nitrido without an appended crown, spans 4 units of charge. Bounds for the p K a values of the transient imido complexes were used with the Mn(VI/V) reduction potentials to calculate the N-H BDFEs of the imidos in acetonitrile. Despite a span of >700 mV and >9 p K a units across the series, the hydrogen atom BDFE only spans ∼6 kcal/mol (between 73 and 79 kcal/mol). These results suggest that the incorporation of cationic functionalities is an effective strategy for accessing wide ranges of reduction potentials and p K a values while minimally affecting the BDFE, which is essential to modulating electron, proton, or hydrogen atom transfer pathways.

Mycobacterial membrane protein large 3 (Mmpl3) as a trehalose monomycolate lipid transporter contributes to cell wall biosynthesis. Inhibition of Mmpl3 can suppress cell growth and lead to mycobacterial death. SQ109 is a hydrophobic inhibitor of Mmpl3. We have devised a detergent-free strategy to characterize the SQ109/Mmpl3 interaction using the Native Cell Membrane Nanoparticles (NCMN) system, a new method for extracting membrane proteins that better retains native lipids. The homogeneity of the Mmpl3 NCMN particles was confirmed with electron microscopy. The hydrophobic protein-ligand interaction analysis shown for Mmpl3 using the NCMN system may broadly apply to other membrane proteins., (Copyright © 2021. Published by Elsevier B.V.)

Background: Carbon dots (CDs) are widely used in cell imaging due to their excellent optical properties, biocompatibility and low toxicity. At present, most of the research on CDs focuses on biomedical application, while there are few studies on the application of microbial imaging., Results: In this study, B- and N-doped carbon dots (BN-CDs) were prepared from citric acid, ethylenediamine, and boric acid by microwave hydrothermal method. Based on BN-CDs labeling yeast, the dead or living of yeast cell could be quickly identified, and their growth status could also be clearly observed. In order to further observe the morphology of yeast cell under different lethal methods, six methods were used to kill the cells and then used BN-CDs to label the cells for imaging. More remarkably, imaging of yeast cell with ultrasound and antibiotics was significantly different from other imaging due to the overflow of cell contents. In addition, the endocytosis mechanism of BN-CDs was investigated. The cellular uptake of BN-CDs is dose, time and partially energy-dependent along with the involvement of passive diffusion. The main mechanism of endocytosis is caveolae-mediated., Conclusion: BN-CDs can be used for long-term stable imaging of yeast, and the study provides basic research for applying CDs to microbiol imaging., (© 2021. The Author(s).)

Lipase from Thermomyces lanuginosus (TLL) has been covalently immobilized on heterofunctional octyl-vinyl agarose. That way, the covalently immobilized enzymes will have identical orientation. Then, it has blocked using hexyl amine (HEX), ethylenediamine (EDA), Gly and Asp. The initial activity/stability of the different biocatalysts was very different, being the most stable the biocatalyst blocked with Gly. These biocatalysts had been utilized to analyze if the enzyme activity could decrease differently along thermal inactivation courses depending on the utilized substrate (that is, if the enzyme specificity was altered during its inactivation using 4 different substrates to determine the activity), and if this can be altered by the nature of the blocking agent and the inactivation conditions (we use pH 5, 7 and 9). Results show great changes in the enzyme specificity during inactivation (e.g., activity versus triacetin was much more quickly lost than versus the other substrates), and how this was modulated by the immobilization protocol and inactivation conditions. The difference in the changes induced by immobilization and inactivation were confirmed by fluorescence studies. That is, the functional and structural analysis of partially inactivated immobilized enzyme showed that their inactivation pathway is strongly depended on the support features and inactivation conditions., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Asymmetric mesoporous silica nanoparticles (AMSNs) with one side featuring a spiky nanotopography, while the other side is smooth and solid, were synthesized via an ethylenediamine (EDA)-directed silica-polymer cooperative assembly approach. By simply varying the EDA amount ( x ), AMSNs- x samples with adjustable spiky surface coverage were obtained. It is demonstrated that a spiky coverage higher than 50% improved the hemocompatibility of AMSN- x , possibly due to the reduced contact area of the smooth side exposed to the red blood cell (RBC) membrane. Moreover, AMSNs- 175 and AMSNs- 200 with high spiky coverage enhanced their plasmid DNA (pDNA) loading and binding capability, as well as cellular uptake into HEK-293T cells, thus resulting in high transfection performance. The good hemocompatibility and high performance in pDNA delivery of AMSNs- x with high spiky coverage allow them to serve as promising nonviral vectors for potential applications in gene therapies and DNA vaccines.

While bones have the innate capability to physiologically regenerate, in certain cases regeneration is suboptimal, too slow, or does not occur. Biomaterials-based growth factor delivery systems have shown potential for the treatment of challenging bone defects, however, achieving controlled growth factor release remains a challenge. The objective of this study was to develop a thermally responsive hydrogel for bone regeneration capable of ultrasound-triggered on-demand delivery of therapeutic agents. Furthermore, it was hypothesized that incorporation of hydroxyapatite (HA) into the hydrogel could increase sonosensitization, augmenting ultrasound sensitivity to enable controlled therapeutic release to the target tissue. Alginate thermally responsive P(Alg-g-NIPAAm) hydrogels were fabricated and varying quantities of HA (1, 3, 5, and 7% wt./vol.) incorporated. All hydrogels were highly injectable (maximum injection force below 6.5 N) and rheological characterization demonstrated their ability to gel at body temperature. The study demonstrated the ultrasound-triggered release of sodium fluorescein (NaF), bovine serum albumin (BSA), and bone morphogenetic protein 2 (BMP-2) from the hydrogels. Release rates of BSA and BMP-2 were significantly enhanced in the HA containing hydrogels, confirming for the first time the role of HA as a son sensitizer. Together these results demonstrate the potential of these ultrasound-triggered thermally responsive hydrogels for on-demand delivery of therapeutic agents for bone regeneration., (© 2021 The Authors. Journal of Biomedical Materials Research Part B: Applied Biomaterials published by Wiley Periodicals LLC.)

A high-performance polyacid ion exchange (IEX) nanofiber membrane was used in membrane chromatography for the recovery of lysozyme from chicken egg white (CEW). The polyacid IEX nanofiber membrane (P-BrA) was prepared by the functionalization of polyacrylonitrile (PAN) nanofiber membrane with ethylene diamine (EDA) and bromoacetic acid (BrA). The adsorption performance of P-BrA was evaluated under various operating conditions using Pall filter holder. The results showed that optimal conditions of IEX membrane chromatography for lysozyme adsorption were 10% (w/v) of CEW, pH 9 and 0.1 mL/min. The purification factor and yield of lysozyme were 402 and 91%, respectively. The adsorption process was further scaled up to a larger loading volume, and the purification performance was found to be consistent. Furthermore, the regeneration of IEX nanofiber membrane was achieved under mild conditions. The adsorption process was repeated for five times and the adsorption capacity of adsorber was found to be unaffected., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Despite the common use of salens and hydroxyquinolines as therapeutic and bioactive agents, their metal complexes are still under development. Here, we report the synthesis of novel mixed-ligand metal complexes (MSQ) comprising salen (S), derived from (2,2'-{1,2-ethanediylbis[nitrilo(E) methylylidene]}diphenol, and 8-hydroxyquinoline (Q) with Co(II), Ni(II), Cd(II), Al(III), and La(III). The structures and properties of these MSQ metal complexes were investigated using molar conductivity, melting point, FTIR, 1 H NMR, 13 C NMR, UV-VIS, mass spectra, and thermal analysis. Quantum calculation, analytical, and experimental measurements seem to suggest the proposed structure of the compounds and its uncommon monobasic tridentate binding mode of salen via phenolic oxygen, azomethine group, and the NH group. The general molecular formula of MSQ metal complexes is [M(S)(Q)(H 2 O)] for M (II) = Co, Ni, and Cd or [M(S)(Q)(Cl)] and [M(S)(Q)(H 2 O)]Cl for M(III) = La and Al, respectively. Importantly, all prepared metal complexes were evaluated for their antimicrobial and anticancer activities. The metal complexes exhibited high cytotoxic potency against human breast cancer (MDA-MB231) and liver cancer (Hep-G2) cell lines. Among all MSQ metal complexes, CoSQ and LaSQ produced IC 50 values (1.49 and 1.95 µM, respectively) that were comparable to that of cisplatin (1.55 µM) against Hep-G2 cells, whereas CdSQ and LaSQ had best potency against MDA-MB231 with IC 50 values of 1.95 and 1.43 µM, respectively. Furthermore, the metal complexes exhibited significant antimicrobial activities against a wide spectrum of both Gram-positive and -negative bacterial and fungal strains. The antibacterial and antifungal efficacies for the MSQ metal complexes, the free S and Q ligands, and the standard drugs gentamycin and ketoconazole decreased in the order AlSQ > LaSQ > CdSQ > gentamycin > NiSQ > CoSQ > Q > S for antibacterial activity, and for antifungal activity followed the trend of LaSQ > AlSQ > CdSQ > ketoconazole > NiSQ > CoSQ > Q > S. Molecular docking studies were performed to investigate the binding of the synthesized compounds with breast cancer oxidoreductase (PDB ID: 3HB5). According to the data obtained, the most probable coordination geometry is octahedral for all the metal complexes. The molecular and electronic structures of the metal complexes were optimized theoretically, and their quantum chemical parameters were calculated. PXRD results for the Cd(II) and La(III) metal complexes indicated that they were crystalline in nature., Competing Interests: The authors declare no conflict of interest.

By using solid targets in medical cyclotrons, it is possible to produce large amounts of 68 GaCl 3 . Purification of Ga 3+ from metal ion impurities is a critical step, as these metals compete with Ga 3+ in the complexation with different chelators, which negatively affects the radiolabeling yields. In this work, we significantly lowered the level of iron (Fe) impurities by adding ascorbate in the purification, and the resulting 68 GaCl 3 could be utilized for high-yield radiolabeling of clinically relevant DOTA-based tracers. 68 GaCl 3 was cyclotron-produced and purified with ascorbate added in the wash solutions through the UTEVA resins. The 68 Ga eluate was analyzed for radionuclidic purity (RNP) by gamma spectroscopy, metal content by ICP-MS, and by titrations with the chelators DOTA, NOTA, and HBED. The 68 GaCl 3 eluate was utilized for GMP-radiolabeling of the DOTA-based tracers DOTATOC and FAPI-46 using an automated synthesis module. DOTA chelator titrations gave an apparent molar activity (AMA) of 491 ± 204 GBq/µmol. GMP-compliant syntheses yielded up to 7 GBq/batch [ 68 Ga]Ga-DOTATOC and [ 68 Ga]Ga-FAPI-46 (radiochemical yield, RCY ~ 60%, corresponding to ten times higher compared to generator-based productions). Full quality control (QC) of 68 Ga-labelled tracers showed radiochemically pure and stable products at least four hours from end-of-synthesis.

Overexpression of collagenase, elastase, and tyrosinase is caused by external factors such as ultraviolet (UV) radiation and stress, resulting in wrinkle formation and freckles through the loss of skin elasticity and skin pigmentation. In this study, we developed novel carbon quantum dots (CQDs) with antioxidant and anti-aging properties using tannic acid as a carbon source through a simple microwave-assisted pyrolysis method. The synthesized tannic acid-derived CQDs (T-CQDs) showed bright blue fluorescence (QY = 28.2 ± 4.0%), exhibiting maximum emission at 430 nm under 350 nm excitation. Even though small amount of the T-CQDs (3 μ g ml -1 ) was used, they exhibited excellent free radical scavenging ability (82.8 ± 4.3%). Also, the T-CQDs (10 μ g ml -1 ) revealed remarkable inhibitory activity against skin aging-related collagenase (77.6 ± 4.8%), elastase (52.6 ± 1.0%), and tyrosinase (44.2 ± 1.3%), demonstrating their antioxidant and anti-aging effects. Furthermore, their antioxidant and anti-aging properties were superior to those of tannic acid, L-ascorbic acid, and quercetin used as positive controls. Finally, the T-CQDs effectively suppressed UV-induced reactive oxygen species generation by 30% at the cellular levels and showed high cell viability (99.7 ± 0.8%) even at 500 μ g ml -1 . These results demonstrate that the T-CQDs with superior antioxidant, anti-aging properties, and low cytotoxicity can be utilized as novel anti-aging materials in cosmetic and nanomedicine fields., (© 2021 IOP Publishing Ltd.)

Water pollution originating from organic dyes is endangering the survival and development of society; however, adsorbents with high capacity (>5000 mg g -1 ) for the fast removal (≤30 min) of Congo Red (CR) in aqueous solution have been not reported to date. In the present work, an acid-base stably layered MOF, [Cd(H 2 L)(BS) 2 ] n ·2nH 2 O (L-MOF-1, H 2 L = N1,N2-bis(pyridin-3-ylmethyl)ethane-1,2-diamine, BS = benzenesulfonate), was hydrothermally prepared. L-MOF-1 exhibited high-performance adsorption of CR in aqueous solution at room temperature. The experimental adsorption capacity of the L-MOF-1 adsorbent towards CR reached up to about 12 000 mg g -1 in 20 min in the pH range of 2.2-4.7, which is the best adsorbent with the highest capacity and fastest adsorption of CR to date. The spontaneous adsorption process can be described by the pseudo-second-order kinetic and Langmuir isotherm models. Meanwhile, the L-MOF-1 absorbent possessed a highly positive zeta potential in acid condition (even at pH = 2.2, zeta potential = 36.2 mV). Its good adsorption performance mainly originates from its strong electrostatic attraction with CR in acidic condition, together with diverse hydrogen bonds and ππ stacking interactions. Furthermore, the L-MOF-1 absorbent exhibited good selectivity and could be reused five times through simply washing, where its adsorption efficiency was hardly affected. Therefore, L-MOF-1 is a potential absorbent for effectively removing CR from dye wastewater.

A rapid, low-cost, and selective method for simultaneous and direct determination of maneb group residues (containing ethylenebis and propylenebis dithiocarbamates) in fruit by liquid chromatography coupled to tandem mass spectrometry was developed and validated in the current study. The results showed the maneb group could be melt and stabilized by 5 v% ethylenediamine for 60 days keeping in conventional refrigerators, in which a stable and ionizable pentadentate ligand complex was considered to be formed by the bidentate diamine and sulfhydryl followed by Density Functional Theory calculation. The validated method showed a sensitive quantification limits (0.03 mg/kg), a steady recovery (82.1%-91.0%) and an excellent precision (2.7%-4.3% RSD). This method is applied to analyze fruit samples and achieved satisfactory results. Therefore, this method can be proposed as a robust analytical method of maneb group in fruit, and can be adapted to detect other compounds with sulfhydryl group., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

An assay to detect carbon monoxide (CO), one of the gaseous signaling molecules, has been prepared using a new palladium complex probe. The ethylenediamine group linked to the naphthalimide fluorophore coordinates to Pd(II) which intramolecularly quenches the emission. Upon treatment with CO, the absorbance of the turn-on fluorescent sensor changes due to the formation of a complex between Pd(II) and CO at room temperature in a phosphate buffer. As the concentration of CO increases, the probe peak emission intensity at 527 nm gradually increases. Other analyte controls, such as K + , Mg 2+ , Al 3+ , Zn 2+ , Cr 3+ , Hg 2+ , Fe 3+ , alanine, glycine, leucine, lysine, serine, threonine, tyrosine, F - , Cl - , Br - , NO, NO 2 - , NO 3 - , HCO 3 - , CH 3 COO - , H 2 O 2 , • OH, and t BuOO • , exhibit no significant effect on emission intensity. The response time of the probe to CO was quite fast because of the relatively weak coordination of Pd(II) to the pendent ethylenediamine group. The Pd probe is capable of detecting CO in aqueous buffer as well as in living cells with high selectivity and stability, providing a potential real-time indicator for studying CO-involved reactions in biological systems.

This study reports preparation and physicochemical characterization of natural antimicrobials (Origanum Syriacum essential oil (OSEO), shrimp chitosan nanoparticles (CSNPs)) and new imidazolium ionic liquid-supported Zn(II)Salen. These antimicrobials were separately or co-encapsulated by CSNPs to fabricate novel antimicrobial nanoplatforms "NPFs" (OSEO-loaded CSNPs (NPF-1), Zn(II)Salen-loaded CSNPs (NPF-2), and Zn(II)Salen@OSEO-loaded CSNPs (NPF-3)). The finding of loading, encapsulation, and antimicrobial release studies confirm the suitability of CSNPs for nanoencapsulation of Zn(II)Salen and OSEO. All NPFs can significantly suppress the growth of microbial species with performances dependent upon the microbial strain and nanoplatform concentration. The susceptibility of microbes toward new antimicrobials was as follows; Gram-positive bacteria > Gram-negative bacteria > fungi. The amazing physicochemical features of new nanoplatforms and their bioactive ingredients (Zn(II)Salen, OSEO, and CSNPs) signify the importance of our designs for developing a new generation of nanopharmaceuticals supported both natural products and biogenic ionic metal cofactors, targeting the multidrug resistant (MDR) pathogens., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Herein, the fabrication of a fascinating multifunctional cyclodextrin (CD) chiral stationary phase and its chiral separation performance in capillary electrochromatography are proposed. A facile interfacial polymerization was used to anchor ethanediamine-β-cyclodextrin (EDA-β-CD) polymerized with trimesoyl chloride (TMC) and to form the chiral stationary phase (CSP) composite onto the surface wall of the capillary. The characters of prepared columns were confirmed by Fourier transform infrared spectroscopy (FT-IR), X-ray Photoelectron Spectrometer (XPS), scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDS). This novel CSP offers multi-typical interactions including hydrogen bonding, π-interaction, hydrophobic and electrostatic interaction as well as steric effects which contribute to prominent chiral recognition for Dansyl-DL-amino acids in CEC modes. The EDA-β-CD modified column showed eminent enantioseparation performance towards five Dansyl-DL-amino acids (the DL-forms of valine, threonine, leucine, phenylalanine, serine). Besides, the prepared columns were perfectly reproducible and stable. The relative standard deviations of the enantiomer retention times for intra-day (n = 5), inter-day (n = 3) runs and column-to-columns (n = 3) are below 0.54%, 1.35% and 4.89%, individually. This innovative chiral stationary phase shows a broader application view and scope in chiral recognition domain., Competing Interests: Declaration of Competing Interest Authors declare no conflict of interest., (Copyright © 2021. Published by Elsevier B.V.)

Two new aminodiphosphonic acids derived from salicylic acid and its phosphonic analogue were prepared through a simple and efficient synthesis. 2-[(2-Amino-2,2-diphosphono)ethyloxy]-benzoic acid 8 and 2-[(2-amino-2,2-diphosphono)ethyloxy]-5-ethyl-phenylphosphonic acid 9 were evaluated for their applicability as 68 Ga binding bone-seeking agents. Protonation constants of 8 and 9 and stability constants of the Ga 3+ complexes with 8 and 9 in water were determined. The stability constant of Ga 3+ complex with fully phosphorylated acid 9 (log K GaL = 31.92 ± 0.32) significantly exceeds stability constant of Ga 3+ complex with 8 (log K GaL = 26.63 ± 0.24). Ligands 8 and 9 are as effective for Ga 3+ cation binding as ethylenediamine- N , N' -diacetic- N , N' -bis(methy1enephosphonic) acid and ethylenediamine- N , N , N' , N' -tetrakis(methylenephosphonic) acid, respectively. The labelling process and stability of [ 68 Ga]Ga- 8 and [ 68 Ga]Ga- 9 were studied. Both 8 and 9 readily form 68 Ga-complexes stable to ten-fold dilution with saline. However, in fetal bovine serum, only [ 68 Ga]Ga- 9 was stable enough to be subject to biological evaluation. It was injected into rats with bone pathology and aseptic inflammation of soft tissues. For [ 68 Ga]Ga- 9 in animals with a bone pathology model in 60 and 120 min after injection, a slight accumulation in the pathology site, stable blood percentage level, and moderate accumulation in the liver were observed. For animals with an aseptic inflammation, the accumulation of [ 68 Ga]Ga- 9 in the pathology site was higher than that in animals with bone pathology. Moreover, the accumulation of [ 68 Ga]Ga- 9 in inflammation sites was more stable than that for [ 68 Ga]Ga-citrate. The percentage of [ 68 Ga]Ga- 9 in the blood decreased from 3.1% ID/g (60 min) to 1.5% ID/g (120 min). Accumulation in the liver was comparable to that obtained for [ 68 Ga]Ga-citrate.

We investigated the aluminium-salen complex MBR-8 as a potential anti-cancer agent. To see apoptotic effects induced by MBR-8, alone and in combination with common cytostatic drugs, DNA-fragmentations were studied using the flow cytometric analysis. Western blot analysis and measurement of the mitochondrial membrane potential with a JC-1 dye were employed to identify the pathway of apoptosis. An impressive overcoming of multidrug-resistance in leukemia (Nalm6) cells was observed. Additionally, solid tumor cells including Burkitt-like lymphoma (BJAB) and mamma carcinoma cells (MCF-7) are affected by MBR-8 in the same way. Western blot analysis revealed activation of caspase-3. MBR-8 showed very pronounced selectivity with regard to tumor cells and high synergistic effects in Nalm6 and daunorubicin-resistant Nalm6 cells when administered in combination with vincristine, daunorubicin and doxorubicin. The aluminium-salen complex MBR-8 showed very promising anti-cancer properties which warrant further development towards a cytostatic agent for future chemotherapy. Studies on aluminium compounds for cancer therapy are rare, and our report adds to this important body of knowledge.

The low cost β-zeolite and ethylenediamine modified β-zeolite (EDA@β-zeolite) were prepared by self-assembly method and used for Cu(II) removal from contaminated aqueous solution. Removal ability of β-zeolite toward Cu(II) was greatly improved after ethylenediamine (EDA) modification, the removal performance was greatly affected by environmental conditions. XPS results illustrated that the amide group played important role in the removal process by forming complexes with Cu(II). The EDA@β-zeolite showed desirable recycling ability. The finding herein suggested that the proposed composite is a promising and suitable candidate for the removal of Cu(II) from contaminated natural wastewater and aquifer.