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Emerging contaminants, such as the hormone 17α-ethynylestradiol (EE), in aquatic environments pose a serious risk to both human and environmental health, making efficient removal essential. This study evaluated the effectiveness of three-dimensional porous carbon structures derived from poly(acrylic acid) (PAAc, Carbopol 990) as adsorbents for removing EE from aqueous solutions. Activated carbon materials were prepared using varying ratios of KOH as an activating agent (PAAc : KOH; 1 : 0 AAC, 1 : 1 AC1, 1 : 2 AC2, and 1 : 3 AC3). Adsorption tests were conducted by adding 10 mg of the adsorbent to 40 mL of an EE solution (100 ppm, 20 % acetonitrile in water). Analyses including TGA, XRD, and Raman spectroscopy were performed to evaluate the materials' structural properties and adsorption capacities. Among the materials, AC3 exhibited the highest adsorption capacity for EE (238 mg g -1 ), followed by AC2 (153 mg g -1 ) and AC1 (82 mg g -1 ). The superior efficiency of AC3 can be attributed to its larger surface area and pore volume, enabling greater interaction with EE molecules. These materials demonstrated higher adsorption capacities compared to commercial activated carbons and single-walled carbon nanotubes. This work opens new possibilities for developing efficient adsorbents, contributing to more effective and sustainable solutions for water purification and environmental protection., (© 2024 Wiley-VCH GmbH.)

The Zika virus (ZIKV) is a global health threat due to its rapid spread and severe health implications, including congenital abnormalities and neurological complications. Differentiating ZIKV from other arboviruses such as dengue virus (DENV) is crucial for effective diagnosis and treatment. This study presents the development of a biosensor for detecting the ZIKV non-structural protein 1 (NS1) using gold nanoparticles (AuNPs) functionalized with monoclonal antibodies employing dynamic light scattering (DLS). The biosensor named ZINS1-mAb-AuNP exhibited specific binding to the ZIKV NS1 protein, demonstrating high colloidal stability indicated by a hydrodynamic diameter (D H ) of 140 nm, detectable via DLS. In the absence of the protein, the high ionic strength medium caused particle aggregation. This detection method showed good sensitivity and specificity, with a limit of detection (LOD) of 0.96 μg mL -1 , and avoided cross-reactivity with DENV2 NS1 and SARS-CoV-2 spike proteins. The ZINS1-mAb-AuNP biosensor represents a promising tool for the early and accurate detection of ZIKV, facilitating diagnostic and treatment capabilities for arboviral infections., (© 2024 Wiley-VCH GmbH.)

Leishmaniasis, a critical Neglected Tropical Disease caused by Leishmania protozoa, represents a significant global health risk, particularly in resource-limited regions. Conventional treatments are effective but suffer from serious limitations, such as toxicity, prolonged treatment courses, and rising drug resistance. Herein, we highlight the potential of inorganic nanomaterials as an innovative approach to enhance Leishmaniasis therapy, aligning with the One Health concept by considering these treatments' environmental, veterinary, and public health impacts. By leveraging the adjustable properties of these nanomaterials─including size, shape, and surface charge, tailored treatments for various diseases can be developed that are less harmful to the environment and nontarget species. We review recent advances in metal-, oxide-, and carbon-based nanomaterials for combating Leishmaniasis, examining their mechanisms of action and their dual use as standalone treatments or drug delivery systems. Our analysis highlights a promising yet underexplored frontier in employing these materials for more holistic and effective disease management.

Due to the unprecedented and ongoing nature of the coronavirus outbreak, the development of rapid immunoassays to detect severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and its highly contagious variants is an important and challenging task. Here, we report the development of polyclonal antibody-functionalized spherical gold nanoparticle biosensors as well as the influence of the nanoparticle sizes on the immunoassay response to detect the SARS-CoV-2 spike protein by dynamic light scattering. By monitoring the increment in the hydrodynamic diameter (ΔD H ) by dynamic light scattering measurements in the antigen-antibody interaction, SARS-CoV-2 S-protein can be detected in only 5 min. The larger the nanoparticles, the larger ΔD H in the presence of spike protein. From adsorption isotherm, the calculated binding constant ( K D ) was 83 nM and the estimated limit of detection was 13 ng/mL (30 pM). The biosensor was stable up to 90 days at 4 °C. Therefore, the biosensor developed in this work could be potentially applied as a fast and sensible immunoassay to detect SARS-CoV-2 infection in patient samples., Competing Interests: 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 article., (© 2022 Elsevier Ltd. All rights reserved.)

Mass testing for the diagnosis of COVID-19 has been hampered in many countries owing to the high cost of genetic material detection. This study reports on a low-cost immunoassay for detecting SARS-CoV-2 within 30 min using dynamic light scattering (DLS). The immunosensor comprises 50-nm gold nanoparticles (AuNPs) functionalized with antibodies against SARS-CoV-2 spike glycoprotein, whose bioconjugation was confirmed using transmission electron microscopy (TEM), UV-Vis spectroscopy, Fourier transform infrared spectroscopy (FTIR), and surface-enhanced Raman scattering spectroscopy (SERS). The specific binding of the bioconjugates to the spike protein led to an increase in bioconjugate size, with a limit of detection (LOD) 5.29 × 10 3 TCID 50 /mL (Tissue Culture Infectious Dose). The immunosensor was also proven to be selective upon interaction with influenza viruses once no increase in size was observed after DLS measurement. The strategy proposed here aimed to use antibodies conjugated to AuNPs as a generic platform that can be extended to other detection principles, enabling technologies for low-cost mass testing for COVID-19., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The data provided in this study are related to the fabrication of two light-responsive systems based on reduced graphene oxide (rGO) functionalized with the polymers Pluronic P123 (P123), rGO-P123, and polyethyleneimine (PEI), rGO-PEI, and loaded with amphotericin B (AmB), an antileishmanial drug. Here are described the experimental design to obtain the systems and characterization methods, such as Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR-FTIR), Raman Spectroscopy, Powder X-Ray Diffraction, Transmission Electron Microscopy, Scanning Electron Microscopy and Thermogravimetric Analyses. Also, AmB spectroscopy studies are described. The materials rGO-P123 and rGO-PEI were loaded with AmB and the optimization of AmB and polymer fragments structures revealed several possible hydrogen bonds formed between the materials and the drug. The drug release was analyzed with and without Near-Infrared (NIR) light. In the studies conducted under NIR light irradiation for 10 min, an infrared lamp was disposed at 64 cm from the samples and an optical fiber thermometer was employed to measure the temperature variation. Cytotoxicity studies and antiproliferative assays against Leishmania amazonensis promastigotes were evaluated. The complete work data entitled Amphotericin-B-Loaded Polymer-Functionalized Reduced Graphene Oxides for Leishmania amazonensis Chemo-Photothermal Therapy have been published to Colloids and Surfaces B: Bionterfaces (https://doi.org/10.1016/j.colsurfb.2021.112169) [1]., Competing Interests: 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., (© 2022 The Author(s). Published by Elsevier Inc.)

Two platforms based on reduced graphene oxide (rGO) functionalized with Pluronic® P123 (rGO-P123) and polyethyleneimine - PEI (rGO-PEI) polymers and loaded with amphotericin B (AmB) were fabricated and tested against Leishmania amazonensis, which can cause cutaneous and diffuse cutaneous leishmaniasis. The materials rGO-P123 and rGO-PEI were efficiently loaded with AmB - a polyene antibiotic - which resulted in rGO-P123-AmB (0.078 mg per mg of material) and rGO-PEI-AmB (0.086 mg per mg of material). Under near-infrared (NIR) light irradiation, the amount of AmB released from rGO-PEI-AmB at pH 5.0 and 7.4 doubled in comparison to AmB released in the absence of NIR light under identical conditions. It was accompanied by a photothermal effect. Otherwise, rGO-P123-AmB did not show a significant change in AmB released in the presence and absence of NIR light. Cytotoxicity studies in mammalian host macrophages revealed that rGO-PEI and rGO-PEI-AmB were nontoxic to the host cells, whereas rGO-123 and rGO-P123-AmB were very toxic, particularly the latter. Therefore, only rGO-PEI and rGO-PEI-AmB were tested against L. amazonensis promastigotes in the presence and absence of NIR light. In vitro antiproliferative effects revealed that rGO-PEI-AmB showed a more pronounced activity against the parasite than rGO-PEI, which was improved under NIR light irradiation. Scanning-transmission electron microscopy of L. amazonensis promastigotes after incubation with rGO-PEI or rGO-PEI-AmB suggested autophagic and necrotic cell death. Thus, the facile synthesis, high AmB loading capacity and good photothermal effect make the rGO-PEI-AmB platform a promising candidate for the topical treatment of cutaneous leishmaniasis., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Herein a 1D Co(II) coordination polymer of formula [Co(η 1 -L1)(η 2 -L1)(py) 2 (H 2 O)] n (CoCP) has been synthesised using the rigid H2L1 proligand, containing a long spacer bearing two triple bonds. Single-crystal X-ray diffraction showed that Co(II) adopts a distorted octahedral geometry. The state-averaged complete active self-consistent field (SA-CASSCF) calculation showed that the ground state of CoCP is a high spin quartet with a highly multiconfigurational character of its electronic structure. Due to the large intra- and intermolecular distances between the spin carriers, the magnetic interactions are negligible and the zero-field splitting (ZFS) effects of cobalt(II) ions are predominant. This behavior was confirmed by direct current (DC) magnetic measurements and theoretical calculations using the broken-symmetry approach. Quantum chemical calculations indicate that CoCP has a negative axial component possessing mixed tri-axial anisotropy. The DC magnetic susceptibility data were fitted with a Griffith-Figgis Hamiltonian and the obtained parameters are in good agreement with those simulated by the ab initio calculation. Alternating current (AC) magnetic measurements showed a field induced slow magnetic relaxation in CoCP, which is attributed to the hyperfine interaction effects.

In this work, we report the synthesis and structural characterisation of the ligand 2-(pyridin-3-yl)-benzo[ de ]isoquinoline-1,3(2 H )-dione, 5, its isostructural Werner complexes ML 4 (NCS) 2 (L = 5; M = Co(II) and Ni(II)), and five clathrates with three aromatic guests, ML 4 (NCS) 2 ·2G (M = Co(II) and Ni(II), G = nitrobenzene (NB); M = Co, G = 1,2-dichlorobenzene (1,2-DCB); M = Co(II) and Ni(II), G = o -xylene (OX)). 5 was prepared in high yield by condensation in the solid-state (C 3 S 3 , Cocrystal Controlled Solid-State Synthesis). The Werner complexes ML 4 (NCS) 2 (M = Co(II) and Ni(II)) (apohosts) were prepared by reacting M(NCS) 2 (M = Co(II) and Ni(II)) and 5 in 1-butanol at 60 °C for 24 h. The Werner clathrates were prepared by reacting M(NCS) 2 (M = Co(II) and Ni(II)), G and 5 in 1-butanol at 60 °C for 48-96 h. The clathrates were observed to transform to the apohost ML 4 (NCS) 2 upon heating. CoL 4 (NCS) 2 ·2NB was subsequently regenerated by exposing CoL 4 (NCS) 2 to liquid NB at 60 °C for 48 h. This phase change occurred as a single-crystal to single-crystal phase transformation and was studied by single crystal X-ray diffraction, powder X-ray diffraction and thermal analyses. Structural analyses of the apohost CoL 4 (NCS) 2 and its Werner clathrate CoL 4 (NCS) 2 ·2NB indicated that rotational freedom of the Co-N bonds together with torsional flexibility of the ligand between the imide bond and the pyridine moiety are key to enabling the structural switching induced by exposure to NB or its removal.

A thermally stable carbocationic covalent organic network (CON), named RIO-70 was prepared from pararosaniline hydrochloride, an inexpensive dye, and triformylphloroglucinol in solvothermal conditions. This nanoporous organic material has shown a specific surface area of 990 m 2  g -1 and pore size of 10.3 Å. The material has CO 2 uptake of 2.14 mmol g -1 (0.5 bar), 2.7 mmol g -1 (1 bar), and 6.8 mmol g -1 (20 bar), the latter corresponding to 3 CO 2 molecules adsorbed per pore per sheet. It is shown to be a semiconductor, with electrical conductivity (σ) of 3.17×10 -7  S cm -1 , which increases to 5.26×10 -4  S cm -1 upon exposure to I 2 vapor. DFT calculations using periodic conditions support the findings., (© 2020 Wiley-VCH GmbH.)

The Cu(ii) heptanuclear complex (Cu7atac) was synthesised using the hydrated amino acid ligand 2-(5-amino-1H-1,2,4-triazol-3-yl)acetic acid (Hatac·H2O). Single crystal X-ray diffraction analysis revealed a μ3-hydroxo bridged Cu(ii) heptanuclear complex, consisting of two triangular subunits and one Cu(ii) ion as a bridge with the formula [Cu7(atac)6(μ3-OH)2(NO3)2(H2O)10](NO3)4. The magnetic behaviour of this discrete 0D complex shows strong antiferromagnetic couplings between Cu(ii) mediated by N,N bonding and an anti-anti modes of the carboxylate anion of the ligand atac-. The magnetic data were fitted considering a 3J model. To support the model used to fit the magnetic data of the Cu7atac complex, theoretical calculation methods (complete active space self-consistent field, CASSCF, density functional theory (DFT) using the UKS TPSS/Def2-TZVP//Def2-SVP level and periodic boundary conditions (PBC) using PBE/DZVP-MOLOPT-GTH) were performed to obtain the spin states, spin density map and J couplings. The theoretical results suggest that Cu7atac is a spin-frustrated complex in the ground state, in which the doublet spin state co-exists with the quartet spin state.

Here we describe the assembly and pH-driven operation of two nanocarriers based on non-functionalized (MCM-41) and carboxylate-functionalized (MCM-41-COOH) containers loaded with the anticancer drug doxorubicin (DOX) and capped by quaternary ammonium pillar[5]arene (P[5]A) nanogates. MCM-41 and MCM-41-COOH containers were synthesized and transmission and scanning electron microscopies showed nanoparticles with spherical morphology and dimensions of 85 ± 13 nm. The nanochannels of MCM-41 loaded with DOX were gated through the electrostatic interactions between P[5]A and the silanolate groups formed at the silica-water interface, yielding the MCM-41-DOX-P[5]A nanocarrier. The second nanocarrier was gated through the electrostatic interactions between the carboxylate groups mounted on the surface of MCM-41 and P[5]A, resulting in the MCM-41-COO-DOX-P[5]A nanocarrier. The DOX release profiles from both nanocarriers were investigated by UV-vis spectroscopy at different pH values (2.0, 5.5 and 7.4) and also in the presence of ions, such as citrate 3- (19 mmol L -1 ) and Zn 2+ (1.2 and 50 mmol L -1 ) at 37 °C. MCM-41-COO-DOX-P[5]A can be turned on and off eight times through the formation and breaking of electrostatic interactions. In vitro studies show that MCM-41-COO-DOX-P[5]A can penetrate and release DOX in the nucleus of human breast adenocarcinoma MCF-7 cancer cells leading to a pronounced cytotoxic effect. Therefore, the fabricated nanocarrier based on a water-soluble cationic pillar[5]arene nanogate, which is reversibly opened and closed by electrostatic interactions, can be considered as a promising drug transport and delivery technique for future cancer therapy.

Polyaniline-decorated ZIF-8 nanoparticles (nPANI@nZIF-8) were easily synthesized and employed as a multifunctional system for the delivery of the antitumor drug 5-fluorouracil (5-FU). Because of the storage ability of the network ZIF-8, 68% of the total amount of the 5-FU drug was released at pH 5.2. The system exhibits absorption in the near-infrared (NIR) region and can be used in the photothermal therapy owing to the presence of nPANI, which has a strong NIR uptake. This absorption causes local hyperthermia by aiding in the diffusion of the drug molecules contained by the polymer into nPANI@nZIF-8/5-FU achieving a greater release of the 5-FU drug, about 80% activated by an NIR laser (λ = 980 nm). This hyperthermia reached about 70 °C (200 μL, 1 mg mL -1 nPANI@nZIF-8), which was directly proportional to the concentration of the material. Therefore, our work can aid in the construction of new chemo-photothermal platforms that may be employed in cancer therapy., Competing Interests: The authors declare no competing financial interest.

Background: A deeper knowledge on the effects of the degradation of magnetic nanoparticles on their magnetic properties is required to develop tools for the identification and quantification of magnetic nanoparticles in biological media by magnetic means., Methods: Citric acid and phosphonoacetic acid-coated magnetic nanoparticles have been degraded in a medium that mimics lysosomal conditions. Magnetic measurements and transmission electron microscopy have been used to follow up the degradation process., Results: Particle size is reduced significantly in 24 h at pH 4.5 and body temperature. These transformations affect the magnetic properties of the compounds. A reduction of the interparticle interactions is observed just 4 h after the beginning of the degradation process. A strong paramagnetic contribution coming from the degradation products appears with time., Conclusions: A model for the in vivo degradation of magnetic nanoparticles has been followed to gain insight on the changes of the magnetic properties of iron oxides during their degradation. The degradation kinetics is affected by the particle coating, in our case being the phosphonoacetic acid-coated particles degraded faster than the citric acid-coated ones.

Adsorption of CO2 on MCM-41 functionalised with [3-(2-aminoethylamino)propyl]trimethoxysilane (MCM-41-N2), N(1)-(3-trimethoxysilylpropyl)diethylenetriamine (MCM-41-N3), 4-aminopyridine (MCM-41-aminopyridine), 4-(methylamino)pyridine (MCM-41-methylaminopyridine) and 1,5,7-triazabicyclo[4.4.0]dec-5-ene (MCM-41-guanidine) was investigated. The amine-functionalised materials were characterised by (29)Si and (13)C solid-state nuclear magnetic resonance, N2 adsorption/desorption isotherms, X-ray diffraction and transmission electron microscopy. CO2 adsorption at 1.0 bar and 30 °C showed that the amount of CO2 (nads/mmol g(-1)) adsorbed on MCM-41-N2 and MCM-41-N3 is approximately twice the amount adsorbed on MCM-41. For MCM-41-aminopyridine, MCM-41-methylaminopyridine and MCM-41-guanidine, the CO2 adsorption capacity was smaller than that of MCM-41 at the same conditions. The proton affinity (computed with wB97x-D/6-311++G(d,p)) of the secondary amino groups is higher than that of the primary amino groups; however, the relative stabilities of the primary and secondary carbamates are similar. The differential heat of adsorption decreases as the number of secondary amino groups increases.

The interaction between CO2 and 1,2-diaminoethane was computed using pure and hybrid density functionals. The CAM-B3LYP and wB97X-D functionals using a triple-ζ basis set that includes diffuse and polarization functions are the best functionals for calculating the relative energies of the zwitterion intermediate compared to a coupled-cluster with a single, double and non-iterative triple excitation (CCSD(T)) approach extrapolated to a complete basis set limit. With the two functionals and the triple-ζ basis set, the zwitterion is 1.70 kcal mol(-1) less stable than the reactants, and close to 1.63 kcal mol(-1) computed using the CCSD(T) approach. The inclusion of vibrational and thermal corrections and of entropic effects increases the relative energy of the zwitterion to 14.7 kcal mol(-1). Bending of the CO2 geometry increases its acidity due to a 1.09 eV reduction in the LUMO energy. Calculation of the CO2 interaction energy with a set of amines revealed that the interaction energies show a high correlation with their basicities, with the stronger bases stabilizing the zwitterion. For the most basic amine computed (3,4,6,7,8,9-hexahydro-2H-pyrimido[1,2-a]pyrimidine), the Gibbs free energy of the zwitterion is 15.8 kcal mol(-1) lower than the reactants. Therefore, for this highly basic amine, the zwitterion may have a longer lifetime, in contrast to 2-aminoethanol (MEA), where it is only a transient species.

Two series of flexible dicyanomethylene compounds, specifically, class 1 and class 2 compounds, have been designed and synthesised. In class 1 compounds, the dicyanomethylene groups are separated by glycol chain spacers of different lengths, whereas, in class 2 compounds, the spacers are alkyl linkers of different lengths. The notion underlying the design of these compounds is that in class 1 molecules, the spacers contain donor oxygen atoms that could not only form hydrogen bonds during the course of crystal packing but also promote withdrawing effects that modify the photophysical and electrochemical properties of these molecules in solution; in contrast, these effects would be absent for class 2 molecules. However, this study revealed that, with respect to crystal packing, the size of the spacers and their even and odd numbers of atoms are more important than their chemical nature. All of the synthesised compounds exhibited blue emission in the solid state and in CH2Cl2 solutions. The photophysical and electrochemical properties of these compounds in solution were not significantly affected by the type and length of the spacer that was used in each molecule. In the solid state, however, the compound with the shortest spacer showed the highest Stokes shift. The electronic transitions for the synthesized compounds in solution were explained by density functional theory and time-dependent density functional theory calculations, which indicated that the methylene moieties control the properties of both classes of compounds and that the spacers do not conjugate with the end groups. These two series of flexible dicyanomethylene compounds could be utilised as molecular building blocks for the development of new solids with novel properties.

In the title mol-ecule, C(18)H(18)O(5), the two aromatic rings are connected by a flexible 3-oxapentane chain. The mol-ecule has a crystallographic twofold rotation axis (C(2)) passing through the central O atom. An intra-molecular C-H⋯O hydrogen bond is observed in the solid state.

Two dendrimers were designed and synthesized that contain a 1,3,5-trisubstituted benzenoid core and incorporate 9 and 21 viologen (4,4'-bipyridinium) units in their branches in addition to hydrophilic (aryloxy) terminal groups. For comparison purposes, model compounds containing one and two viologen units were also studied. These polycationic dendrimers form strong host-guest complexes with the dianionic form of the red dye eosin in dilute CH(2)Cl(2) solutions. Titration experiments, based on fluorescence measurements, showed that each viologen unit in the dendritic structures becomes associated with an eosin dianion. Electrochemical (in MeCN) and photosensitization (in CH(2)Cl(2)) experiments revealed that only a fraction of the viologen units present in the dendritic structures can be reduced. This fraction corresponds to the number of viologen units present in the outer shells of the dendrimers. The reasons for incomplete charge pooling are discussed. Comparison with the behavior of polyviologen dendrimers that are terminated with bulky tetraarylmethane groups and were studied previously enabled the role played by the terminal groups in the redox and hosting properties to be elucidated.

Inspired by the concept of multivalency in living systems, two mechanically interlocked molecules have been conceived that incorporate not once or twice but thrice the features of a pH-switchable [2]rotaxane with two orthogonal recognition sites for dibenzo[24]crown-8 (DB24C8), and 2,3-dinaphtho[24]crown-8 (DN24C8)-one a dialkylammonium ion (CH(2)NH(2)(+)CH(2)) and the other a bipyridinium dication (BIPY(2+)). Whereas at low pH, the CH(2)NH(2)(+)CH(2) sites bind the DB24C8/DN24C8 macrocycles preferentially, at high pH, deprotonation occurs with loss of hydrogen bonding and the macrocycles will move to the BIPY(2+) sites, where they can acquire some stabilizing [pi-pi] stacking interactions. Such mechanically interlocked molecules have been assembled from a trifurcated rig-like component wherein the dumbbell-like components of three [2]rotaxanes have one of their ends fused onto alternate positions (1,3,5) around a benzenoid core. The rig is mechanically interlocked by a platform based on a tritopic receptor, wherein either three benzo[24]crown-8 or three 2,3-naphtho[24]crown-8 macrocycles are fused onto a hexaoxatriphenylene core. The synthesis of these molecular elevators involves 1:1 complexation, followed by stoppering, i.e., feet are added to the rig. (1)H NMR spectroscopy and cyclic voltammetry, aided and abetted by absorption spectroscopy, have been employed to unravel the details of the mechanism by which the rig and platform components move on the alternate addition of base and acid. For each molecular elevator, the platform operates by taking three distinct steps associated with each of the three deprotonation/reprotonation processes. Thus, molecular elevators are more reminiscent of a legged animal than they are of passengers on freight elevators.