Measuring local pH in electrochemistry

Localized pH measurements are important in various areas of electrochemistry, from corrosion to bio-electrochemistry and electrocatalysis. Different techniques are available to perform these measurements and offer numerous possibilities in terms of spatial and temporal resolution, sensitivity, and precision. In this brief review we present the recent progress made and summarize the main techniques available for localized pH measurements in electrochemistry such as scanning probe techniques (SECM, SICM, SIET), laser (confocal) fluorescence microscopy, rotating ring-disc electrode (RRDE) voltammetry, and infra-red spectroscopy, among others.     

Isoflavonoid-Antibiotic Thin Films Fabricated by MAPLE with Improved Resistance to Microbial Colonization

Staphylococcus aureus (Gram-positive) and Pseudomonas aeruginosa (Gram-negative) bacteria represent major infectious threats in the hospital environment due to their wide distribution, opportunistic behavior, and increasing antibiotic resistance. This study reports on the deposition of polyvinylpyrrolidone/antibiotic/isoflavonoid thin films by the matrix-assisted pulsed laser evaporation (MAPLE) method as anti-adhesion barrier coatings, on biomedical surfaces for improved resistance to microbial colonization. The thin films were characterized by Fourier transform infrared spectroscopy, infrared microscopy, and scanning electron microscopy. In vitro biological assay tests were performed to evaluate the influence of the thin films on the development of biofilms formed by Gram-positive and Gram-negative bacterial strains. In vitro biocompatibility tests were assessed on human endothelial cells examined for up to five days of incubation, via qualitative and quantitative methods. The results of this study revealed that the laser-fabricated coatings are biocompatible and resistant to microbial colonization and biofilm formation, making them successful candidates for biomedical devices and contact surfaces that would otherwise be amenable to contact transmission.     

Studies on thermal,spectral, magnetic and biological properties of new Ni(II), Cu(II) and Zn(II) complexes with a bismacrocyclic ligand bearing an aromatic linker

Novel complexes of M₂LCl₄·nH₂O type (M:Ni, n = 4; M:Cu, n = 3 and M:Zn, n = 0; L: ligand resulted from 1,4-phenylenediamine, 3,6-diazaoctane-1,8-diamine and formaldehyde one-pot condensation) were synthesized and characterised by microanalytical, ESI–MS, IR, UV–Vis, ¹H NMR and EPR spectra, magnetic data at room temperature and molar conductivities as well. The electrochemical behaviour of complexes was investigated by cyclic voltammetry. Simultaneous TG/DTA measurements were performed in order to evidence the thermal behaviour of the obtained complexes. Processes such as water elimination, fragmentation and oxidative degradation of the organic ligand as well as chloride elimination occurred during thermal decomposition. The antimicrobial assays demonstrate that the compounds exhibited good antibacterial activity, especially against S. aureus and E. coli strains, the most active being the copper(II) complex, which also exhibited the most prominent anti-biofilm effect, suggesting its potential use for the development of new antimicrobial agents. The biological activity was correlated with log P _ow values. All complexes disrupt the membrane integrity of HCT 8 tumour cells.     

Thermal behaviour of some novel antimicrobials based on complexes with a Schiff base bearing 1,2,4-triazole pharmacophore

A series of complexes of type [ML(CH₃COO)(OH₂)₂] (M: Co, Ni; HL: 2-[(E)-1H-1,2,4-triazol-3-ylimino)methyl]phenol)) and [M₂L₂(CH₃COO)₂(OH₂)_n] (M: Cu, n = 2; M: Zn, n = 0) were synthesised by template condensation. The compounds were characterised with microanalytical, ESI–MS, IR, electronic, EPR spectra and magnetic data at room temperature. Based on the IR and ESI–MS spectra, a dinuclear structure with the acetate as bridge was proposed for Cu(II) and Zn(II) complexes. The dinuclear structure of Cu(II) complex is also consistent with both magnetic behaviour and EPR spectrum. The thermal analyses have evidenced processes as water elimination, acetate decomposition, as well as oxidative degradation of the Schiff base. The final decomposition product was the most stable metal oxide as indicated by powder X-ray diffraction. The cobalt and copper compounds exhibited a broad spectrum of antibacterial activity towards both planktonic and biofilm-embedded cells. The complexes exhibit a low cytotoxicity except for Cu(II) species that induces the early apoptosis for the HEp 2 cells.     

Multivalent Recognition of Concanavalin A by {Mo132} Glyconanocapsules—Toward Biomimetic Hybrid Multilayers

Herein, we consider Müller’s spherical, porous, anionic, molybdenum oxide based capsule, (NH₄)₄₂‐ [{(Mo^VI)Mo^VI₅O₂₁(H₂O)₆}₁₂{Mo^V₂O₄(CH₃COO)}₃₀]?10 CH₃COONH₄? 300 H₂O≡(NH₄)₄₂? 1 a ?crystal ingredients≡ 1 , {Mo₁₃₂}, as an effective sugar‐decorated nanoplatform for multivalent lectin recognition. The ion‐exchange of NH₄⁺ ions of 1 with cationic‐sugars, D ‐mannose‐ammonium chloride ( 2 ) or D ‐glucose‐ammonium chloride ( 3 ) results in the formation of glyconanocapsules (NH₄)_42?n 2 _n? 1 a and (NH₄)_42?m 3 _m? 1 a . The Mannose (NH₄)_42?n 2 _n? 1 a capsules bind selectively Concanavalin A (Con A) in aqueous solution, giving an association avidity constant of ${K{{{\rm multi}\hfill \atop {\rm a}\hfill}}}$ =4.6×10⁴ M ^?1 and an enhancement factor of β=K${{{{\rm multi}\hfill \atop {\rm a}\hfill}}}$ /K${{{{\rm mono}\hfill \atop {\rm ass}\hfill}}}$ =21.9, reminiscent of the formation of “glycoside clusters” on the external surface of glyconanocapsule. The glyconanocapsules (NH₄)_42?n 2 _n? 1 a and (NH₄)_42?m 3 _m? 1 a self‐assemble in “hybrid multilayers” by successive layer‐by‐layer deposition of (NH₄)_42?n 2 _n? 1 a or (NH₄)_42?m 3 _m? 1 a and Con A. These architectures, reminiscent of versatile mimics of artificial tissues, can be easily prepared and quantified by using quartz crystal microgravimetry (QCM). The “biomimetic hybrid multilayers” described here are stable under a continual water flow and they may serve as artificial networks for a greater depth of understanding of various biological mechanisms, which can directly benefit the fields of chemical separations, sensors or storage‐delivery devices.     

Electrical properties study of multi-walled carbon nanotubes/hybrid-glass nanocomposites

Electrical properties of multi-walled carbon nanotubes (MWNTs)/hybrid-glass nanocomposites prepared by the fast-sol–gel reaction were investigated in light of percolation theory. A good correlation was found between the experimental results and the theory. We obtained a percolation threshold ? _c  = 0.22 wt%, and a critical exponent of t = 1.73. These values are reported for the first time for a silica-based system. The highest conductivity measured on the MWNT/hybrid-glass nanocomposites was σ ≈ 10^?3(Ω cm)^?1 for 2 wt% carbon nanotube (CNT) loading. The electrical conductivity was at least 12 orders of magnitude higher than that of pure silica. Electrostatic force microscopy and conductive-mode atomic force microscopy studies demonstrated conductivity at the micro-level, which was attributed to the CNT dispersed in the matrix. It appears that the dispersion in our MWNT/hybrid-glass system yields a particularly low percolation threshold compared with that of a MWNT/silica-glass system. Materials with electrical conductivities described in this work can be exploited for anti-static coating.     

Two Possible Strategies for Drug Modification of Gemcitabine and Future Contributions to Personalized Medicine

Drug repurposing is an emerging strategy, which uses already approved drugs for new medical indications. One such drug is gemcitabine, an anticancer drug that only works at high doses since a portion is deactivated in the serum, which causes toxicity. In this review, two methods were discussed that could improve the anticancer effect of gemcitabine. The first is a chemical modification by conjugation with cell-penetrating peptides, namely penetratin, pVEC, and different kinds of CPP6, which mostly all showed an increased anticancer effect. The other method is combining gemcitabine with repurposed drugs, namely itraconazole, which also showed great cancer cell inhibition growth. Besides these two strategies, physiologically based pharmacokinetic models (PBPK models) are also the key for predicting drug distribution based on physiological data, which is very important for personalized medicine, so that the correct drug and dosage regimen can be administered according to each patient’s physiology. Taking all of this into consideration, it is believed that gemcitabine can be repurposed to have better anticancer effects.     

An Edible Oil Enriched with Lycopene from Pink Guava (Psidium guajava L.) Using Different Mechanical Treatments

According to the regulations of the United States Food and Drug Administration (FDA), organic solvents should be limited in pharmaceutical and food products due to their inherent toxicity. For this reason, this short paper proposes different mechanical treatments to extract lycopene without organic solvents to produce an edible sunflower oil (SFO) enriched with lycopene from fresh pink guavas (Psidium guajava L.) (FPGs). The methodology involves the use of SFO and a combination of mechanical treatments: a waring blender (WB), WB+ high-shear mixing (HSM) and WB+ ultrafine friction grinding (UFFG). The solid:solvent (FPG:SFO) ratios used in all the techniques were 1:5, 1:10 and 1:20. The results from optical microscopy and UV–vis spectroscopy showed a correlation between the concentration of lycopene in SFO, vegetable tissue diameters and FPG:SFO ratio. The highest lycopene concentration, 18.215 ± 1.834 mg/g FPG, was achieved in WB + UFFG with an FPG:SFO ratio of 1:20. The yield of this treatment was 66% in comparison to the conventional extraction method. The maximal lycopene concentration achieved in this work was significantly higher than the values reported by other authors, using high-pressure homogenization for tomato peel and several solvents such as water, SFO, ethyl lactate and acetone.     

Iboga Inspired N-Indolylethyl-Substituted Isoquinuclidines as a Bioactive Scaffold: Chemoenzymatic Synthesis and Characterization as GDNF Releasers and Antitrypanosoma Agents

The first stage of the drug discovery process involves the identification of small compounds with biological activity. Iboga alkaloids are monoterpene indole alkaloids (MIAs) containing a fused isoquinuclidine-tetrahydroazepine ring. Both the natural products and the iboga-inspired synthetic analogs have shown a wide variety of biological activities. Herein, we describe the chemoenzymatic preparation of a small library of novel N-indolylethyl-substituted isoquinuclidines as iboga-inspired compounds, using toluene as a starting material and an imine Diels–Alder reaction as the key step in the synthesis. The new iboga series was investigated for its potential to promote the release of glial cell line-derived neurotrophic factor (GDNF) by C6 glioma cells, and to inhibit the growth of infective trypanosomes. GDNF is a neurotrophic factor widely recognized by its crucial role in development, survival, maintenance, and protection of dopaminergic neuronal circuitries affected in several neurological and psychiatric pathologies. Four compounds of the series showed promising activity as GDNF releasers, and a leading structure (compound 11) was identified for further studies. The same four compounds impaired the growth of bloodstream Trypanosoma brucei brucei (EC₅₀ 1–8 μM) and two of them (compounds 6 and 14) showed a good selectivity index.