Highly Selective Ratiometric Sensors for Pb2+ Based on Luminescent Zn(II)-Coordination Polymers with Thiophenedicarboxylate. Crystal Structures and Spectroscopic Studies.

The development of luminescent coordination polymers for the selective sensing of Pb2+ in water constitutes an active area of research that impacts analytical, environmental, and inorganic chemistry. Herein, two novel water-stable 2D Zn-coordination polymers {[Zn2(H2O)2(tdc)2(bpy)]·(H2O)}n 1 and [Zn(tdc)(tmb)]n 2 (tdc = thiophenedicarboxylate; bpy = 4,4'-bipyridine and tmb = 4,4'-trimethylenebipyridine) were synthesized, structurally determined by single crystal X-ray diffraction, and studied in-depth as luminescent sensors for a series of cations (Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+ Cd2+, Hg2+ and Pb2+) in 20% aqueous ethanol. These Zn-polymers possess photostability in 20% aqueous ethanol with a strong emission at 410 upon excitation at 330 nm and quantum yields of around Φ = 0.09. Under these conditions, Pb+2 can be efficiently sensed with polymer 2 through a fluorescent ratiometric response with selectivity over common interfering metal ions such as Cu2+, Cd2+ and Hg2+ in the micromolar concentration range (detection limit = 1.78 ± 10 µM). Such selectivity/affinity of Pb2+ over Hg2+ for luminescent chemosensors is still rare. On the basis of spectroscopic tools (1H NMR, far ATR-IR, PXRD), the X-ray crystal structure of 2, and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopic analysis, the ratiometric fluorescent response is proposed via an efficient metal-ion exchange driven through interactions between thiophenedicarboxylate rings and Pb2+ ions. The use of flexible luminescent Zn-coordination polymers as sensors for selective and direct detection of Pb2+ in aqueous media has been unexplored until now.

Biogeneration of silver nanoparticles from Cuphea procumbens for biomedical and environmental applications.

Nanotechnology is one of the most important and relevant disciplines today due to the specific electrical, optical, magnetic, chemical, mechanical and biomedical properties of nanoparticles. In the present study we demonstrate the efficacy of Cuphea procumbens to biogenerate silver nanoparticles (AgNPs) with antibacterial and antitumor activity. These nanoparticles were synthesized using the aqueous extract of C. procumbens as reducing agent and silver nitrate as oxidizing agent. The Transmission Electron Microscopy demonstrated that the biogenic AgNPs were predominantly quasi-spherical with an average particle size of 23.45 nm. The surface plasmonic resonance was analyzed by ultraviolet visible spectroscopy (UV-Vis) observing a maximum absorption band at 441 nm and Infrared Spectroscopy (FT IR) was used in order to structurally identify the functional groups of some compounds involved in the formation of nanoparticles. The AgNPs demonstrated to have antibacterial activity against the pathogenic bacteria Escherichia coli and Staphylococcus aureus, identifying the maximum zone of inhibition at the concentration of 0.225 and 0.158 µg/mL respectively. Moreover, compared to the extract, AgNPs exhibited better antitumor activity and higher therapeutic index (TI) against several tumor cell lines such as human breast carcinoma MCF-7 (IC50 of 2.56 µg/mL, TI of 27.65 µg/mL), MDA-MB-468 (IC50 of 2.25 µg/mL, TI of 31.53 µg/mL), human colon carcinoma HCT-116 (IC50 of 1.38 µg/mL, TI of 51.07 µg/mL) and melanoma A-375 (IC50 of 6.51 µg/mL, TI of 10.89 µg/mL). This fact is of great since it will reduce the side effects derived from the treatment. In addition, AgNPs revealed to have a photocatalytic activity of the dyes congo red (10-3 M) in 5 min and malachite green (10-3 M) in 7 min. Additionally, the degradation percentages were obtained, which were 86.61% for congo red and 82.11% for malachite green. Overall, our results demonstrated for the first time that C. procumbens biogenerated nanoparticles are excellent candidates for several biomedical and environmental applications.

Antimicrobial Activity of Biogenic Silver Nanoparticles from Syzygium aromaticum against the Five Most Common Microorganisms in the Oral Cavity.

Syzygium aromaticum (clove) has been used as a dental analgesic, an anesthetic, and a bioreducing and capping agent in the formation of metallic nanoparticles. The main objective of this study was to evaluate the antimicrobial effect in oral microorganisms of biogenic silver nanoparticles (AgNPs) formed with aqueous extract of clove through an ecofriendly method "green synthesis". The obtained AgNPs were characterized by UV-Vis (ultraviolet-visible spectroscopy), SEM-EDS (scanning electron microscopy-energy dispersive X-ray spectroscopy), TEM (transmission electron microscopy), and ζ potential, while its antimicrobial effect was corroborated against oral Gram-positive and Gram-negative microorganisms, as well as yeast that is commonly present in the oral cavity. The AgNPs showed absorption at 400-500 nm in the UV-Vis spectrum, had an average size of 4-16 nm as observed by the high-resolution transmission electron microscopy (HR-TEM), and were of a crystalline nature and quasi-spherical form. The antimicrobial susceptibility test showed inhibition zones of 2-4 mm in diameter. Our results suggest that AgNPs synthesized with clove can be used as effective growth inhibitors in several oral microorganisms.

EGF-Coupled Gold Nanoparticles Increase the Expression of CNPase and the Myelin-Associated Proteins MAG, MOG, and MBP in the Septal Nucleus Demyelinated by Cuprizone.

Current pharmacological therapies against demyelinating diseases are not quite satisfactory to promote remyelination. Epidermal growth factor (EGF) can expand the population of oligodendrocyte precursor cells (OPCs) that may help with the remyelination process, but its delivery into the injured tissue is still a biomedical challenge. Gold nanoparticles (GNPs) may be a useful tool for drug delivery into the brain. To evaluate remyelination in the septal nucleus, we administered intracerebral GNPs coupled with EGF (EGF-GNPs). C57BL6/J mice were demyelinated with 0.4% cuprizone (CPZ) and divided into several groups: Sham, Ctrl, GNPs, EGF, and EGF-GNPs. We evaluated the remyelination process at two time-points: 2 weeks and 3 weeks post-injection (WPI) of each treatment. We used the rotarod for evaluating motor coordination. Then, we did a Western blot analysis myelin-associated proteins: CNPase, MAG, MOG, and MBP. EGF-GNPs increase the expression of CNPase, MAG, and MOG at 2 WPI. At 3 WPI, we found that the EGF-GNPs treatment improves motor coordination and increases MAG, MOG, and MBP. EGF-GNPs enhance the expression of myelin-associated proteins and improve the motor coordination in mice. Thus, EGF-associated GNPs may be a promising pharmacological vehicle for delivering long-lasting drugs into the brain.

Silver Nanoparticles from Annona muricata Peel and Leaf Extracts as a Potential Potent, Biocompatible and Low Cost Antitumor Tool.

Cancer is one of the most prevalent diseases in the world and requires new therapies for its treatment. In this context, the biosynthesis of silver nanoparticles (AgNPs) has been developed to treat different types of tumors. The Annona muricata plant is known for having anticancer activity. Its main compounds present in the leaves, stems and skin, allowing for its use as reducing agents. In this manuscript, AgNPs with leaf extract (AgNPs-LE) and fruit peel extract (AgNPs-PE) of A. muricata were biosynthesized obtaining an average nanoparticle diameter sizes smaller than 50 nm, being 19.63 ± 3.7 nm and 16.56 ± 4.1 nm, and with a surface plasmonic resonance (SPR) at 447 and 448 nm, respectively. The lactone functional group present in the LE and PE extracts was identified by the FTIR technique. The behavior and antiproliferation activity of AgNPs-LE and AgNPs-PE were evaluated in breast, colon and melanoma cancer cell lines. Our results showed that Annona muricata fruit peel, which is a waste product, has an antitumor effect more potent than leaf extract. This difference is maintained with AgNPs where the destruction of cancer cells was, for the first time, achieved using concentrations that do not exceed 3 µg/mL with a better therapeutic index in the different tumor strains. In conclusion, we present a low-cost one-step experimental setup to generate AgNPs-PE whose in-vitro biocompatibility and powerful therapeutic effect make it a very attractive tool worth exploiting.

Gold nanoparticles produce transient reactive gliosis in the adult brain.

Gold nanoparticles (GNPs) have unique physical and chemical properties that allow them to function as a drug-delivery system for several tissues: skin, eye, liver, and others. However, information about the biological response of brain tissue against GNPs is limited. Astrocytes and microglia cells are the first line of defense against brain insults and proper indicators of the level of brain damage. This study was aimed to evaluate the astrocytic and microglia response after an intracerebral injection of polyethylene-glycol-coupled GNPs (PEGylated GNPs). We injected spherical PEGylated GNPs (85 × 106 nanoparticles /nl) with a glass micropipette (inner diameter =35 µm) into the striatum of P60 CD1 mice. We evaluated the cellular response of astrocytes and microglia on days 3, 7, 14, 30, and 90 after intracerebral injection. For both astrocytes and microglia cells, our findings indicated that the glial response was transient and mainly circumscribed to the injection site. This evidence suggests that PEGylated GNPs are well-tolerated by the neural tissue. Understanding the effects of GNPs in the adult brain is a crucial step to design proper pharmacological vehicles to deliver long-lasting drugs.

Remineralizing Effect of Xilitol, Juniperus Communis and Camellia Sinensis Added to a Toothpaste: An In Vitro Study / Efecto remineralizante del Xilitol, Juniperus Communis y Camellia Sinensis adicionados en pastas dentales: Estudio in vitro

ABSTRACT The aim of this study was to explore the remineralizing effect of toothpastes based on Xilitol, Camellia Sinensis and Juniperus Communis. An in vitro experimental study was carried out in an 18 human premolars sample, which were treated with one of the 3 evaluated toothpastes and a control fluoride one. The atomic percentages of Ca and P were evaluated by Energy Dispersive X-ray Spectroscopy (EDS). In addition, the enamel surface of treated teeth was visualized by Scanning Electron Microscopy (SEM). The evaluations were carried out in three stages: pre-treatment, after an artificial demineralization process and after the treatment with the toothpastes. In the statistical analysis, the one-way ANOVA and Pearson correlation tests were used. Xilitol and Juniperus Communis showed the greatest gain of P ions compared to the control group (p<0.01). As for Ca, the group treated with xylitol-based toothpaste showed more ion gain compared with the control group (p<0.01). In the Pearson correlation test between Ca and P, statistically significant correlations were observed in all groups (p<0.01), ranging between r=0.7413 (Xylitol Group) and r=0.9510 (Control Group). We concluded that Xylitol paste showed the highest remineralizing property, both in the EDS analysis and in the SEM images.

RESUMEN El objetivo de este studio fue explorer el efecto remineralizante de las cremas dentales compuestas de Xilitol, Camelia Sinensis y Juniperus Communis. Se llevó a cabo un estudio experimental in vitro en una muestra de 18 premolares humanos, los cuales fueron tratados con una de las tres pastas dentales evaluadas y una fluorada. Los porcentajes atomicos de Ca y P fueron evaluados por Espectroscopia de rayos X de energía dispersive (EDS). Además, la superficie del esmalte de los dientes tratados fue examinada por Microscopia Electronica de Barrido (SEM). Las evaluaciones fueron llevadas a cabo en tres etapas: pre-tratamiento, despues de un proceso artificial de desmineralizacion y después del tratamiento con las pastas dentales. Se usaron ANOVA de una via y correlacion de Pearson para el analisis estadistico. Xilitol y Juniperus Communis mostraron la mayor ganancia de iones P comparados con el grupo control (p<0.01), con rangos entre r=0.7413 (Grupo con Xylitol) and r=0.9510 (Group Control). Se concluyó que la pasta con Xilitol mostró las mayores propiedades remineralizantes, tanto en el analisis EDS y las imágenes SEM.

Five Decades of Cuprizone, an Updated Model to Replicate Demyelinating Diseases.

INTRODUCTION: Demyelinating diseases of the central nervous system (CNS) comprise a group of neurological disorders characterized by progressive (and eventually irreversible) loss of oligodendrocytes and myelin sheaths in the white matter tracts. Some of myelin disorders include: Multiple sclerosis, Guillain-Barré syndrome, peripheral nerve polyneuropathy and others. To date, the etiology of these disorders is not well known and no effective treatments are currently available against them. Therefore, further research is needed to gain a better understand and treat these patients. To accomplish this goal, it is necessary to have appropriate animal models that closely resemble the pathophysiology and clinical signs of these diseases. Herein, we describe the model of toxic demyelination induced by cuprizone (CPZ), a copper chelator that reduces the cytochrome and monoamine oxidase activity into the brain, produces mitochondrial stress and triggers the local immune response. These biochemical and cellular responses ultimately result in selective loss of oligodendrocytes and microglia accumulation, which conveys to extensive areas of demyelination and gliosis in corpus callosum, superior cerebellar peduncles and cerebral cortex. Remarkably, some aspects of the histological pattern induced by CPZ are similar to those found in multiple sclerosis. CPZ exposure provokes behavioral changes, impairs motor skills and affects mood as that observed in several demyelinating diseases. Upon CPZ removal, the pathological and histological changes gradually revert. Therefore, some authors have postulated that the CPZ model allows to partially mimic the disease relapses observed in some demyelinating diseases. CONCLUSION: for five decades, the model of CPZ-induced demyelination is a good experimental approach to study demyelinating diseases that has maintained its validity, and is a suitable pharmacological model for reproducing some key features of demyelinating diseases, including multiple sclerosis.

Cadmium-1,4-cyclohexanedicarboxylato coordination polymers bearing different di-alkyl-2,2'-bipyridines: syntheses, crystal structures and photoluminescence studies.

Four coordination polymers have been synthesized using self-assembly solution reactions under ambient conditions, reacting Cd(ii) ions with 1,4-cyclohexanedicarboxylic acid in the presence of different 2,2'-bipyridine co-ligands: {[Cd(H2O)(e,a-cis-1,4-chdc)(2,2'-bpy)]·H2O}n (1); [Cd2(H2O)2(e,a-cis-1,4-chdc)2(4,4'-dmb)2]n (2); {[Cd(e,a-cis-1,4-chdc)(5,5'-dmb)]·H2O·CH3OH}n (3) and {[Cd(e,e-trans-1,4-chdc)(4,4'-dtbb)]·CH3OH}n (4), where 1,4-chdc = 1,4-cyclohexanedicarboxylato, 2,2'-bpy = 2,2'-bipyridine, 4,4'-dmb = 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmb = 5,5'-dimethyl-2,2'-bipyridine and 4,4'-dtbb = 4,4'-di-tert-butyl-2,2'-bipyridine. Crystallographic studies show that compound 1 has a 1D structure propagating along the crystallographic b-axis; the Cd ion in 1 is six-coordinated with a distorted-octahedral coordination sphere. Compound 2 has two crystallographic different Cd ions and both are six-coordinated with a distorted-octahedral coordination sphere. Compound 3 exhibits a seven-coordinated Cd ion having a distinctive distorted-monocapped trigonal prismatic geometry. In compound 4, the Cd ion is also seven-coordinated in a distorted monocapped octahedral geometry. Compounds 2, 3 and 4 possess rhombic-shaped dinuclear units (Cd2O2) as nodes to generate larger cycles made up of four dinuclear units, a Cd4 motif, bridged by four 1,4-chdc ligands, accomplishing, thus, 2D structures. Remarkably, in compound 4 the 1,4-chdc ligand conformation changes to the equatorial, equatorial trans, unlike the other compounds where the bridging ligand conformation is the more typical equatorial, axial cis. The solid state luminescence properties of 1-4 were investigated; polymers 3 and 4 exhibited a strong blue emission (λem = 410-414 nm) compared to 1 and 2; structure-related photoluminescence is attributed to the degree of hydration of the compounds. Furthermore, Cd-polymer 3 suspended in acetone allows the fluorescence selective sensing of acetonitrile over common organic solvents such as alcohols and DMF, based on turn-on fluorescence intensity with a limit of 53 µmol L-1.

Biosynthesis of Silver Nanoparticles on Orthodontic Elastomeric Modules: Evaluation of Mechanical and Antibacterial Properties.

In the present study, silver nanoparticles (AgNPs) were synthesized in situ on orthodontic elastomeric modules (OEM) using silver nitrate salts as metal-ion precursors and extract of the plant Hetheroteca inuloides (H. inuloides) as bioreductant via a simple and eco-friendly method. The synthesized AgNPs were characterized by UV-visible spectroscopy; scanning electron microscopy-energy-dispersive spectroscopy (SEM-EDS) and transmission electron microscopy (TEM). The surface plasmon resonance peak found at 472 nm confirmed the formation of AgNPs. SEM and TEM images reveal that the particles are quasi-spherical. The EDS analysis of the AgNPs confirmed the presence of elemental silver. The antibacterial properties of OEM with AgNPs were evaluated against the clinical isolates Streptococcus mutans, Lactobacillus casei, Staphylococcus aureus and Escherichia coli using agar diffusion tests. The physical properties were evaluated by a universal testing machine. OEM with AgNPs had shown inhibition halos for all microorganisms in comparison with OEM control. Physical properties increased with respect to the control group. The results suggest the potential of the material to combat dental biofilm and in turn decrease the incidence of demineralization in dental enamel, ensuring their performance in patients with orthodontic treatment.

Synthesis of silver nanoparticles using aqueous extracts of Heterotheca inuloides as reducing agent and natural fibers as templates: Agave lechuguilla and silk.

Silver nanoparticles (Ag NPs) were synthesized using a one-pot green methodology with aqueous extract of Heterotheca inuloides as a reducing agent, and the support of natural fibers: Agave lechuguilla and silk. UV-Vis spectroscopy, X-Ray photoelectron spectroscopy XPS and transmission electron microscopy TEM were used to characterize the resulting bionanocomposite fibers. The average size of the Ag NPs was 16nm and they exhibited low polydispersity. XPS studies revealed the presence of only metallic Ag in the nanoparticles embedded in Agave. lechuguilla fibers. Significant antibacterial activities against gram-negative Escherichia coli and gram-positive Staphylococcus aureus were determined. AgO as well as metallic Ag phases were detected when silk threads were used as a substrates hinting at the active role of substrate during the nucleation and growth of Ag NPs. These bionanocomposites have excellent mechanical properties in tension which in addition to the antibacterial properties indicate the potential use of these modified natural fibers in surgical and biomedical applications.

An evaluation of the antibacterial properties and shear bond strength of copper nanoparticles as a nanofiller in orthodontic adhesive.

OBJECTIVES: To evaluate the antibacterial properties and effects of an orthodontic adhesive containing copper nanoparticles (NPs) on the material's shear bond strength. METHODS: Antimicrobial activity was analysed by a disk diffusion test against S. aureus, E. coli and S. mutans. The NPs were added to the orthodontic adhesive at 0.0100 wt%, 0.0075 wt%, and 0.0050 wt%. Sixty extracted bicuspids were divided into two groups and the enamel of all teeth was conditioned with phosphoric acid. A coat of moisture insensitive primer (MIP) was applied prior to the bonding of brackets with composite resin. Group I served as a control and the bonding procedure was performed according to the manufacturer's instructions. Group II comprised the test teeth, into which 0.0100 wt% copper NPs were included in the MIP. Samples were tested and statistically analysed (p ≤ 0.05). The adhesive remnant index (ARI) was also assessed microscopically. - RESULTS: The adhesive with copper NPs showed a bactericidal effect against the bacteria under study. A significantly higher bond strength was obtained with the orthodontic adhesive that included 0.0100 wt% of copper NPs (15.23 ± 6.8 MPa) in comparison with the control group (9.59 ± 4.3 MPa). The ARI scores indicated that the groups were significantly different and strengthened by the incorporation of NPs (p = 0.004). CONCLUSION: The results of the present study suggested that an orthodontic adhesive, which included copper NPs, significantly increased material shear bond strength without adverse side effects on colour and appearance. The adhesive interface was strengthened by homogeneously dispersed copper NPs added as a nanofiller.

Morphological and chemical changes of deciduous enamel produced by Er:YAG laser, fluoride, and combined treatment.

OBJECTIVE: The purpose of this study was to evaluate in vitro morphological and chemical changes on human deciduous enamel produced by Er:YAG laser irradiation, fluoride application, combined treatment, and acid dissolution. BACKGROUND DATA: Er:YAG laser has been proposed as a potential preventive dental caries strategy. There is scarce information regarding deciduous enamel. METHODS: Eighty enamel samples were assigned to eight groups (n=10): G1, control; G2, G3, and G4, Er:YAG laser irradiation at 7.5, 12.7, and 39.8 J/cm(2), respectively; G5, fluoride application; G6, G7, and G8, irradiation at previous densities plus fluoride application. Morphology was evaluated by scanning electron microscopy, and chemical composition was determined by energy dispersive X-ray spectroscopy before treatment (BT), after treatment (AT), and after acid dissolution (AAD). One way and repeated measures analysis of variance (ANOVA) were used (p≤0.05). RESULTS: Morphology of lased surfaces included craters, exposed prisms, fractures, and melting. No morphological modifications appeared after fluoride application, or AAD. Chemically, AT: C atomic percentage (at%) decreased in G3, G4, and G8; O at% decreased in G5-G8; F content was higher for G7; trace elements remained under 1.0 at%; Ca at % increased in G4, G7, and G8; there were increments in P at% in G4 and G8; and Ca/P increased in G4, G7, and G8. AAD: F at% dropped to 0.00 in G5-G8; and P at% increased in G7. CONCLUSIONS: Morphological changes of Er:YAG irradiated enamel represented mild to severe damages. Conditions employed in this study are not recommended for deciduous caries prevention. Er:YAG energy density influenced chemical changes in enamel to enhance its structure. Acid dissolution removed fluoride from enamel surface.