Simultaneous recognition of dopamine and uric acid in real samples through highly sensitive new electrode fabricated using ZnO/carbon quantum dots: bio-imaging and theoretical studies.

Dopamine (DA) and uric acid (UA), which are vital components in human metabolism, cause several health problems if they are present in altered concentrations; thus, the determination of DA and UA is essential in real samples using selective sensors. In the present study, graphite carbon paste electrodes (CPE) were fabricated using ZnO/carbon quantum dots (ZnO/CQDs) and employed as electrochemical sensors for the detection of DA and UA. These electrodes were fully characterized via different analytical techniques (XRD, SEM, TEM, XPS, and EDS). The electrochemical responses from the modified electrodes were evaluated using cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. The results showed that the present electrode has exhibited high sensitivity towards DA, recognizing even at low concentrations (0.12 µM), and no inference was observed in the presence of UA. The ZnO/CQD electrode was applied for the simultaneous detection of co-existing DA and UA in real human urine samples and the peak potential separation between DA and UA was found to be greatly associated with the synergistic effect originated from ZnO and CQDs. The limit of detection (LOD) of the electrode was analyzed, and compared with other commercially available electrodes. Thus, the ZnO/CQD electrode was used to detect DA and UA in real samples, such as Saccharomyces cerevisiae cells.

Synthesis and Nano-Sized Characterization of Bioactive Oregano Essential Oil Molecule-Loaded Small Unilamellar Nanoliposomes with Antifungal Potentialities.

The development of greener nano-constructs with noteworthy biological activity is of supreme interest, as a robust choice to minimize the extensive use of synthetic drugs. Essential oils (EOs) and their constituents offer medicinal potentialities because of their extensive biological activity, including the inhibition of fungi species. However, their application as natural antifungal agents are limited due to their volatility, low stability, and restricted administration routes. Nanotechnology is receiving particular attention to overcome the drawbacks of EOs such as volatility, degradation, and high sensitivity to environmental/external factors. For the aforementioned reasons, nanoencapsulation of bioactive compounds, for instance, EOs, facilitates protection and controlled-release attributes. Nanoliposomes are bilayer vesicles, at nanoscale, composed of phospholipids, and can encapsulate hydrophilic and hydrophobic compounds. Considering the above critiques, herein, we report the in-house fabrication and nano-size characterization of bioactive oregano essential oil (Origanum vulgare L.) (OEO) molecules loaded with small unilamellar vesicles (SUV) nanoliposomes. The study was focused on three main points: (1) multi-compositional fabrication nanoliposomes using a thin film hydration-sonication method; (2) nano-size characterization using various analytical and imaging techniques; and (3) antifungal efficacy of as-developed OEO nanoliposomes against Trichophyton rubrum (T. rubrum) by performing the mycelial growth inhibition test (MGI). The mean size of the nanoliposomes was around 77.46 ± 0.66 nm and 110.4 ± 0.98 nm, polydispersity index (PdI) of 0.413 ± 0.015, zeta potential values up to -36.94 ± 0.36 mV were obtained by dynamic light scattering (DLS). and spherical morphology was confirmed by scanning electron microscopy (SEM). The presence of OEO into nanoliposomes was displayed by attenuated total reflection Fourier-transform infrared (ATR-FTIR) spectroscopy. Entrapment efficiency values of 79.55 ± 6.9% were achieved for OEO nanoliposomes. In vitro antifungal activity of nanoliposomes tested against T. rubrum strains revealed that OEO nanoliposomes exhibited the highest MGI, 81.66 ± 0.86%, at a concentration of 1.5 µL/mL compared to the rest of the formulations. In summary, this work showed that bioactive OEO molecules with loaded nanoliposomes could be used as natural antifungal agents for therapeutical purposes against T. rubrum.

Mononuclear and Tetranuclear Copper(II) Complexes Bearing Amino Acid Schiff Base Ligands: Structural Characterization and Catalytic Applications.

Two new glycine-Schiff base copper(II) complexes were synthesized. Single crystal X-ray diffraction (SCXRD) allowed us to establish the structure of both complexes in the solid state. The glycine-Schiff base copper(II) complex derived from 2'-hydroxy-5'-nitroacetophenone showed a mononuclear hydrated structure, in which the Schiff base acted as a tridentate ligand, and the glycine-Schiff base copper(II) complex derived from 2'-hydroxy-5'-methylacetophenone showed a less common tetranuclear anhydrous metallocyclic structure, in which the Schiff base acted as a tetradentate ligand. In both compounds, copper(II) had a tetracoordinated square planar geometry. The results of vibrational, electronic, and paramagnetic spectroscopies, as well as thermal analysis, were consistent with the crystal structures. Both complexes were evaluated as catalysts in the olefin cyclopropanation by carbene transference, and both led to very high diastereoselectivity (greater than 98%).

Simultaneous recognition of cysteine and cytosine using thiophene-based organic nanoparticles decorated with Au NPs and bio-imaging of cells.

Biomolecules like cysteine and cytosine play a significant role in many physiological processes, and their unusual level in biological systems can lead to many diseases including cancer. Indeed, the need for selective detection of these moieties by a fluorescence probe is imperative. Thus, thiophene based Schiff N,N'-bis(thiophene-2-ylmethylene)thiophenemethane (BMTM) was synthesized and then characterized using several analytical techniques before converting it into organic nanoparticles (ONPs). Then, fluorescent organic inorganic nanohybrids (FONs) were obtained after decorating ONPs with AuNPs to yield BMTM-Au-ONPs (FONPs). The morphology of the particles, analyzed using a Transmission Electron Microscope (TEM), shows that AuNPs were embedded with low density organic matter (ONPs). FONPs were employed to recognize cysteine and cytosine simultaneously. No interference was observed from other moieties such as guanine, uracyl, NADH, NAD, ATP, and adenine during the detection. It means that the intensity of the fluorescence signal was significantly changed (enhanced for cytosine and quenched for cysteine). So, FONPs were used to detect cysteine and cytosine in real samples, like Saccharomyces cerevisiae cells. As expected, no considerable fluorescence signal for cysteine was observed, while for cytosine, strong fluorescence signals were detected in the cells. DFT was used to explain the interaction of FONPs with cysteine or cytosine.

Insulin­like growth factor axis: A potential nanotherapy target for resistant cervical cancer tumors (Review).

Cervical cancer is among the most frequently occurring neoplasms worldwide, and it particularly affects individuals in developing countries. Factors such as the low quality of screening tests, the high incidence of locally advanced cancer stages and the intrinsic resistance of certain tumors are the main causes of failure in the treatment of this neoplasm. Due to advances in the understanding of carcinogenic mechanisms and bioengineering research, advanced biological nanomaterials have been manufactured. The insulin-like growth factor (IGF) system comprises multiple growth factor receptors, including IGF receptor 1. These receptors are activated by binding to their respective growth factor ligands, IGF-1 and IGF-2, and insulin, and play an important role in the development, maintenance, progression, survival and treatment resistance of cervical cancer. In the present review, the role of the IGF system in cervical cancer and three nanotechnological applications that use elements of this system are described, namely Trap decoys, magnetic iron oxide nanoparticles and protein nanotubes. Their use in the treatment of resistant cervical cancer tumors is also discussed.

Effect of the structural integrity on the size and porosity of gold-implanted mixed-metal oxide nanocomposites: their influence on the photocatalytic degradation of thioanisole.

Since the interfacial binding strength and structural integrity have a strong influence on the active sites of nanocomposites, this study focused on exploring the structural and electronic properties at the interface between the implanted metal ion and host support. For this, nanocomposites of gold embedded in CeO2-ZrO2 and CeO2-Al2O3 matrices were fabricated, and their structural and morphological properties were investigated using ICP-OES, UV-vis, XRD, Raman, HRTEM, and high-resolution XPS studies and compared. From the results, it was found that the deposition of gold is highly favored over CeO2-ZrO2 (3.99 atomic %) than CeO2-Al2O3 (1.21 atomic %); however, the same amount of gold was used for the synthesis of both nanocomposites, as befits it. The HRTEM images of Au/CeO2-ZrO2 displayed well-organized yarn textured particles with less than 5 nm size, which lacks in Au/CeO2-Al2O3. The reason for this less systematized and less Au embedding in the presence of alumina in CeO2-Al2O3 was verified with the high-resolution XPS studies of both nanocomposites and an elevated binding energy due to the mobility of Au particles over CeO2-Al2O3 was observed, while for Au/CeO2-ZrO2, a very small binding energy shift of gold states (Au 4f5/2 0.39; Au 4f7/2 0.17 eV) and the CeO2-ZrO2 matrix that favored an increased intermolecular force between gold and the supporting host was observed. This agrees well with UV-vis electronic spectrum analysis, which revealed that the incorporation of gold nanoparticles narrowed the band gap more significantly in Au/CeO2-ZrO2 (4.2 eV) than Au/CeO2-Al2O3 (4.94 eV) suggesting the elevated electron transfer from the conduction band of CeO2-ZrO2 to Au interfaces. In addition, XRD and Raman studies of Au/CeO2-ZrO2 showed a pronounced phase transformation of Ce4+ to Ce3+ in the presence of homovalent Zr4+ ions with an increased structural disorder in CeO2 promoting the localized surface plasmon resonance (LSPR) in the lattice of CeO2-ZrO2, which was less detected in Au/CeO2-Al2O3 due to the interference of less-desired γ-Al2O3 phases. These characteristics of Au/CeO2-ZrO2 ensured its performance as a promised photocatalyst for thioanisole degradation without using any harmful oxidants, and its stability towards different irradiation conditions, such as visible, ultraviolet, and solar light.

Understanding of [RuL(ONO)]n+ acting as nitric oxide precursor, a theoretical study of ruthenium complexes of 1,4,8,11-tetraazacyclo- tetradecane having different substituents: How spin multiplicity influences bond angle and bond lengths (Ru-O-NO) in releasing of NO.

Generation of nitric oxide has been a great interest in cell biology as it involves a wide range of physiological functions including the blood pressure control; thus the exploitation of ruthenium chemistry has been motivated in biochemical and clinical points of view. Herein, the structural and electronic properties of ruthenium(II) complexes of 1,4,8,11-tetraazacyclotetradecane containing pyridyl, imidazole and benzimidazole (L1, L2, L3) were analyzed theoretically in the context of how spin multiplicity plays a crucial role influencing the NO release from the LRu-ONO moiety. The results show that ß-cleavage of nitrito in the complex motivates the release of NO as it depends highly on total spin multiplicity of metal ion altering significantly the geometrical parameters; particularly, a decrease of bond length of Ru-ONO is highly associated with an increase of RuO-NO bond distance that correlates with the decrease of the Ru-O-NO bond angle ultimately leading to the release of NO; apparently, the bending nature of Ru-O-NO defines its release from the complex. This is consistent with orbital energy (dx2-y2) where the stabilization of axial Ru-O bond in the complex was observed, and proved by molecular orbital studies. In the excitation of the complex (singlet to triplet or singlet to quintet), the NO release has been facilitated, agreeing with the Gibbs free energy data where a lower energy for NO release was obtained compared to other types of excitations. In the calculated electronic spectra, a visible broad band with relatively high intensity for [RuL1ONO]+ was observed, agreeing approximately with reported experimental results.

Sunlight powered degradation of pentoxifylline Cs0.5Li0.5FeO2 as a green reusable photocatalyst: Mechanism, kinetics and toxicity studies.

The degradation of Pentoxifylline (PXF) was achieved successfully by green energy in a built-in solar photocatalytic system using hybrid LiCs ferrites (Li0.5Cs0.5FeO2) as magnetically recoverable photocatalysts. Kinetics showed a first-order reaction rate with maximum PXF removal of 94.91% at mildly acidic pH; additionally, the ferromagnetic properties of catalyst allowed recovery and reuse multiple times, reducing costs and time in degradation processes. The degradation products were identified by HPLC-MS and allowed us to propose a thermodynamically feasible mechanism that was validated through DFT calculations. Additionally, toxicity studies have been performed in bacteria and yeast where high loadings of Cs showed to be harmful to Staphylococcus aureus (MIC≥ 4.0 mg/mL); Salmonella typhi (MIC≥ 8.0 mg/mL) and Candida albicans (MIC≥ 10.0 mg/mL). The presented setup shows effectiveness and robustness in a degradation process using alternative energy sources for the elimination of non-biodegradable pollutants.

Glutamine chelation governs the selective inhibition of Staphylococcus aureus and Salmonella typhi growth by cis-dichloro-bis(8-quinolinolato)zirconium(IV): Theory and experiment.

Quinolone-based Schiff base zirconium(IV) complex was studied as potential bacterial inhibitor against Gram-positive Staphylococcus aureus and Gram-negative Salmonella typhi growth, showing that the interaction of the complex with L-glutamine which presents in the membrane of wall leads cell death, and the mode of bacterial interaction was analyzed theoretically by DFT. Furthermore, the interaction of different amino acid residues L-alanine, D-alanine, L-lysine and D-glutamine with the metal complex through UV-vis docking studies was conducted observing that D-glutamine interacts efficiently among other amino acid residues. This observation is consistent with the interaction of the metal complex that was effective when participating in an insight of the peptidoglycan cell wall since the binding nature of glutamine potentially inhibits these microorganisms.

Electrochemical and theoretical studies of the interactions of a pyridyl-based corrosion inhibitor with iron clusters (Fe15, Fe30, Fe45, and Fe60).

The capacity of 2,6-bis[((2-pyridylmethyl)oxy)methyl)]pyridine (BPMMP) to inhibit the corrosion of mild carbon steel in HCl was analyzed. In a polarization study, both the cathodic and anodic currents were appreciably decreased in the presence of BPMMP, suggesting that this ligand is effective at inhibiting corrosion at the metal surface. This conclusion is consistent with the results of impedance analysis, where only one time constant corresponding to one depressed capacitive loop was detected, and the diameter of the impedance plot was directly related to the concentration of BPMMP. Furthermore, when recurrence analysis was performed, a decrease in regular noise was observed due to the change of Shannon entropy when the inhibitor was present in the corrosive medium, showing that a high degree of recurrence increases the entropy of the system. Electrochemical data on some pyridyl-based inhibitors were collected from the literature and used to plot (i) I corr (A/cm2) vs. inhibition efficiency (η%) and (ii) ΔG°ads vs. inhibition efficiency (ƞ%) in order to examine the general relationships between these parameters. Furthermore, the interactions of the ligand BPMMP with different iron clusters (Fe15, Fe30, Fe45, and Fe60) were analyzed theoretically using density functional theory (DFT). The structural and electronic properties of BPMMP and its protonated form BPMMPH+ were studied before and after the interactions of BPMMP with the iron clusters. The first protonation was found to occur at pyridine nitrogen atom N1, resulting in a Gibbs free energy ΔG of -10.2 kcal/mol, with an energy difference of 5.3 kcal/mol between the two possible protonated conformers. Graphical abstract Recurrence and Noise signal performance of BPMMP as corrosion inhibitor.