NIR-Emitting Gold Nanoclusters Encapsulated in PS-b-PEG Polymer Micelles.

Gold nanoclusters (AuNCs) are an emerging type of luminescent probe, featuring good biocompatibility, high photostability, and large Stoke shifts. Their lack of colloidal stability is, however, a drawback for many applications. Here, we report the stabilization of AuNCs emitting in the NIR by a thiol-terminated polystyrene chain (Mn = 5000 g mol-1). The optical properties of this nanocomposite remain invariant for 2 years in THF. To use the PS5k-AuNCs in an aqueous environment, these were encapsulated into polymer micelles using a polystyrene-b-poly(ethylene glycol) copolymer. The resulting hierarchical constructs, with diameters of ca. 125 to 215 nm, have promising properties for applications as luminescent probes such as contrast agents for biomedical imaging.

Molecular Design of a Metal-Nitrosyl Ferroelectric with Reversible Photoisomerization.

The development of photo-responsive ferroelectrics whose polarization may be remotely controlled by optical means is of fundamental importance for basic research and technological applications. Herein, we report the design and synthesis of a new metal-nitrosyl ferroelectric crystal (DMA)(PIP)[Fe(CN)5(NO)] (1) (DMA = dimethylammonium, PIP = piperidinium) with potential phototunable polarization via a dual-organic-cation molecular design strategy. Compared to the parent non-ferroelectric (MA)2[Fe(CN)5(NO)] (MA = methylammonium) material with a phase transition at 207 K, the introduction of larger dual organic cations both lowers the crystal symmetry affording robust ferroelectricity and increases the energy barrier of molecular motions, endowing 1 with a large polarization of up to 7.6 µC cm-2 and a high Curie temperature (Tc) of 316 K. Infrared spectroscopy shows that the reversible photoisomerization of the nitrosyl ligand is accomplished by light irradiation. Specifically, the ground state with the N-bound nitrosyl ligand conformation can be reversibly switched to both the metastable state I (MSI) with isonitrosyl conformation and the metastable state II (MSII) with side-on nitrosyl conformation. Quantum chemistry calculations suggest that the photoisomerization significantly changes the dipole moment of the [Fe(CN)5(NO)]2- anion, thus leading to three ferroelectric states with different values of macroscopic polarization. Such optical accessibility and controllability of different ferroelectric states via photoinduced nitrosyl linkage isomerization open up a new and attractive route to optically controllable macroscopic polarization.

Perylene-Based Coordination Polymers: Synthesis, Fluorescent J-Aggregates, and Electrochemical Properties.

The incorporation of electroactive organic building blocks into coordination polymers (CPs) and metal-organic frameworks (MOFs) offers a promising approach for adding electronic functionalities such as redox activity, electrical conductivity, and luminescence to these materials. The incorporation of perylene moieties into CPs is, in particular, of great interest due to its potential to introduce both luminescence and redox properties. Herein, we present an innovative synthesis method for producing a family of highly crystalline and stable coordination polymers based on perylene-3,4,9,10-tetracarboxylate (PTC) and various transition metals (TMs = Co, Ni, and Zn) with an isostructural framework. The crystal structure of the PTC-TM CPs, obtained through powder X-ray diffraction and Rietveld refinement, provides valuable insights into the composition and organization of the building blocks within the CP. The perylene moieties are arranged in a herringbone pattern, with short distances between adjacent ligands, which contributes to the dense and highly organized framework of the material. The photophysical properties of PTC-Zn were thoroughly studied, revealing the presence of J-aggregation-based and monomer-like emission bands. These bands were experimentally identified, and their behavior was further understood through the use of quantum-chemical calculations. Solid-state cyclic voltammetry experiments on PTC-TMs showed that the perylene redox properties are maintained within the CP framework. This study presents a simple and effective approach for synthesizing highly stable and crystalline perylene-based CPs with tunable optical and electrochemical properties in the solid state.

Impairment of the angiogenic process may contribute to lower success rate of root canal treatments in diabetes mellitus.

AIM: To investigate the association between root canal treatment outcome, diabetes mellitus, and alterations of the angiogenic process. METHODOLOGY: A retrospective observational study was conducted in healthy (control group, CG) and diabetic (type II diabetes mellitus group, DG) patients after root canal treatment. The follow-up appointments were performed to clinically and radiographically observe symptoms, the healing of periapical lesions and the quality of root fillings. In the animal model study, diabetic Goto-Kakizaki (GK) rats and control Wistar rats were used. After 21 days of pulp exposure and the development of apical periodontitis (AP), the mandibles were removed for scintigraphic, radiographic, histopathological and molecular analyses. Chi-square tests were performed to examine the variables related to endodontic outcome and differences between animal groups were assessed using the Student's t-test. RESULTS: The group of patients with diabetes had a significantly lower rate of success following root canal treatment than the CG (p < .001). Logistic regression suggested that diabetes is a risk factor for success of root canal treatment. In the animal study, GK rats had significantly higher fasting glycaemia at t0 and t21 (p < .001) and triglycerides levels (p < .05) and area under the curve (AUC) during the insulin tolerance test at t21 (p < .001). AP area was significantly greater in GK rats (p < .05). Histologically, diabetic rats had increased signs of periodontal ligament inflammation 21 days after the induction of apical periodontitis, with fibro-hyaline matrix filling and vessel with undefined walls. Wistar rats had significantly increased vascular endothelial growth factor (VEGF) levels and VEGF/Ang-2 ratio 21 days after AP induction (p < .08; p < .07). GK rats had intrinsically lower levels of VEGF than control rats (p < .05), which did not change after AP. CONCLUSION: Diabetes mellitus should be considered as an important factor in the prognosis of root canal treatment and its outcomes over time. Future strategies to improve angiogenesis and tissue repair should be pursued to achieve better root canal treatment outcomes in diabetic patients.

Photoresponsive Organic-Inorganic Hybrid Ferroelectric Designed at the Molecular Level.

Molecular ferroelectrics are becoming an important area of research due to their ability to form a variety of structures exhibiting the desired properties. However, the precise control over the assembly of molecular building blocks for the design and synthesis of photoresponsive molecular ferroelectrics remains a considerable challenge. Here, we report a new hybrid high-temperature ferroelectric, (Me2NH2)[NaFe(CN)5(NO)], by judiciously assembling inorganic photochromic nitroprusside anion, as the framework building block, and polar organic cation Me2NH2+, as the dipole-moment carrier, into the crystal lattice. Ferroelectricity arises through the synergetic ordering of Me2NH2+ below 408 K. Piezoresponse force microscopy witnessed the presence of 180° ferroelectric domains and evidenced polarization switching by repeatedly applying an external electric field. Irradiation of the N-bound nitrosyl ligand (ground state) leads to two different conformations: isonitrosyl O-bound (metastable state I) and side-on nitrosyl conformation (metastable state II). Such photoisomerization realized in solid-state molecular ferroelectrics allows for the photoswitching between the ferroelectric ground state and the metastable state. These results pave the way for new design approaches toward developing next-generation photostimulated ferroelectric materials at the molecular level.

Porphyrin-Oligopyridine Triads: Synthesis and Optical Properties.

The synthesis of two triads with two porphyrinyl units linked by oligopyridine derivatives and a new ß-functionalized porphyrin-dihydroazepine is described. One of the porphyrin-oligopyridine triads has a quinquepyridine unit connecting the porphyrins ß-pyrrolic positions, while the other one has an asymmetric quaterpyridine with one of the pyridines fused to the porphyrin. All compounds have fluorescence emission quantum yields in the range of meso-tetraphenylporphyrin (16-22%).

Cryptolepine and quindoline: understanding their photophysics.

Quindoline (QUIND, indolo[3,2-b]quinoline) and cryptolepine (CRYPT, 5-methyl-10H-indolo[3,2-b]quinoline) together with their corresponding derivatives have been studied for decades due to their important biological activity against diseases like malaria. The biological activity of drugs is routinely investigated using fluorescence based methods. However, recent reports show that the photophysics of CRYPT and its analogues is not yet understood. Herein, the photophysics of CRYPT and QUIND is studied in aqueous solutions at different pH values and in both protic and aprotic solvents of different polarities. CRYPT and QUIND are shown to exist in different prototropic forms depending on pH and solvent polarity. CRYPT is found to be more sensitive to the solvent nature. Both compounds are shown to have two-photon stimulated emission. Their two-photon absorption (TPA) cross-sections were measured in the 710-960 nm range. The TPA cross-section is relatively low but allows for the observation of both compounds in HEK 293 T cells, where CRYPT is found mostly in the nucleus and QUIND accumulates in the cytoplasm.

Nonlinear emission of quinolizinium-based dyes with application in fluorescence lifetime imaging.

Charged molecules based on the quinolizinum cation have potential applications as labels in fluorescence imaging in biological media under nonlinear excitation. A systematic study of the linear and nonlinear photophysics of derivatives of the quinolizinum cation substituted by either dimethylaniline or methoxyphenyl electron donors is performed. The effects of donor strength, conjugation length, and symmetry in the two-photon emission efficiency are analyzed in detail. The best performing nonlinear fluorophore, with two-photon absorption cross sections of 1140 GM and an emission quantum yield of 0.22, is characterized by a symmetric D-π-A(+)-π-D architecture based on the methoxyphenyl substituent. Application of this molecule as a fluorescent marker in optical microscopy of living cells revealed that, under favorable conditions, the fluorophore can be localized in the cytoplasmatic compartment of the cell, staining vesicular shape organelles. At higher dye concentrations and longer staining times, the fluorophore can also penetrate into the nucleus. The nonlinearly excited fluorescence lifetime imaging shows that the fluorophore lifetime is sensitive to its location in the different cell compartments. Using fluorescence lifetime microscopy, a multicolor map of the cell is drafted with a single dye.

Smart polymer nanoparticles for high-performance water-borne coatings.

Poly(butyl methacrylate) nanoparticles encapsulating a silica precursor, tetraethoxysilane (TEOS), were synthesized by a two-step emulsion polymerization process. We show that TEOS remains mostly unreacted inside the nanoparticles in water but acts both as a plasticizer and cross-linker in films cast from the dispersions. The diffusion-enhancing plasticizing effect is dominant at annealing temperatures closer to the glass-transition temperature of the polymer, and sol-gel cross-linking reactions predominate at higher temperatures. By choosing an appropriate annealing temperature, we were able to balance polymer interdiffusion and silica cross-linking to obtain films with good mechanical properties and excellent chemical resistance. The hybrid cross-linked films produced from these novel "smart" nanoparticles can be used in water-borne environmentally friendly coatings for high-performance applications.

"Click and go": simple and fast folic acid conjugation.

Folic acid targeting by functionalization of the terminal γ-carboxylic acid is one of the most important strategies to selectively deliver chemotherapeutics and dyes to cancer cells which overexpress folate receptors. However, conjugation of folic acid is limited by its unique solubility and by selectivity issues imposing the need for expensive preparative reverse-phase chromatographic purification to isolate γ-folate conjugates. Herein is provided a novel synthetic tool for the synthesis of new folic acid conjugates with excellent γ-purity based on strain-promoted alkyne-azide cycloadditions with a γ-folate-cyclooctyne conjugate 3. To demonstrate the potential of this methodology several new folate conjugates were synthesized with high γ-purity and without using any type of chromatographic purification by reacting conjugate 3 with several fluorescent probes, polymers and siliceous materials bearing azide. In addition, the cycloaddition reaction between conjugate 3 and an azido-derived fluorescent dye was successfully performed in cellular media leading to an increase of fluorescence in the cells which overexpress folate receptors (NCI-H460).

Pro-Environmental Behaviors: Relationship With Nature Visits, Connectedness to Nature and Physical Activity.

PURPOSE: Examine the association of visits to the natural environment, connectedness to nature, physical activity, and the adoption of pro-environmental behaviors (PEBs) in individuals aged 18 years or older. DESIGN: Cross-sectional study. SETTING: City of Vila Real, located in the north of Portugal. SUBJECTS: We recruited 194 individuals (61 men and 133 women) aged 18-75 years. MESURES: A self-administered questionnaire was used to measure nature visits, connectedness to nature, PEBs, and demographic characteristics. Neighborhood green space was appreciated through a Simplified Land Occupation Map and physical activity was measured using ActiGraph accelerometers (wGT3X-BT). ANALYSIS: Correlations and nonlinear canonical correlation analysis were used to analyze the data. The coefficients of canonical and multiple correlations were calculated. RESULTS: Nature visits were associated with involvement in environmental volunteering (V = .317, P ≤ .05) among men. In these, higher levels of moderate-vigorous PA were associated with green travel behavior (η2 = .325, P ≤ .05). Connectedness with nature was related (P ≤ .05) to private sphere behaviors, such as purchase of eco-products (η2 = .191) and local/seasonal products (η2 = .186) in females and encouraging care and protection of natural environment (η2 = .336, P ≤ .01) in males. CONCLUSIONS: Nature visits, connection to nature, and physical activity levels were related to the adoption of PEBs in the private and public sphere, and these relationships differed between men and women.

Distance to Natural Environments, Physical Activity, Sleep, and Body Composition in Women: An Exploratory Analysis.

A growing body of evidence indicates that living close to nature is associated with better health and well-being. However, the literature still lacks studies analyzing the benefits of this proximity for sleep and obesity, particularly in women. The purpose of this study was to explore how distance to natural spaces is reflected in women's physical activity, sleep, and adiposity levels. The sample consisted of 111 adult women (37.78 ± 14.70). Accessibility to green and blue spaces was assessed using a geographic-information-system-based method. Physical activity and sleep parameters were measured using ActiGraph accelerometers (wGT3X-BT), and body composition was assessed using octopolar bioimpedance (InBody 720). Nonlinear canonical correlation analysis was used to analyze the data. Our findings reveal that women living in green spaces close to their homes had lower levels of obesity and intra-abdominal adiposity. We also demonstrated that a shorter distance to green spaces seemed to correlate with better sleep onset latency. However, no relationship was found between physical activity and sleep duration. In relation to blue spaces, the distance to these environments was not related to any health indicator analyzed in this study.

Multifunctional Nanoparticles with Superparamagnetic Mn(II) Ferrite and Luminescent Gold Nanoclusters for Multimodal Imaging.

Gold nanoclusters (AuNCs) with fluorescence in the Near Infrared (NIR) by both one- and two-photon electronic excitation were incorporated in mesoporous silica nanoparticles (MSNs) using a novel one-pot synthesis procedure where the condensation polymerization of alkoxysilane monomers in the presence of the AuNCs and a surfactant produced hybrid MSNs of 49 nm diameter. This method was further developed to prepare 30 nm diameter nanocomposite particles with simultaneous NIR fluorescence and superparamagnetic properties, with a core composed of superparamagnetic manganese (II) ferrite nanoparticles (MnFe2O4) coated with a thin silica layer, and a shell of mesoporous silica decorated with AuNCs. The nanocomposite particles feature NIR-photoluminescence with 0.6% quantum yield and large Stokes shift (290 nm), and superparamagnetic response at 300 K, with a saturation magnetization of 13.4 emu g-1. The conjugation of NIR photoluminescence and superparamagnetic properties in the biocompatible nanocomposite has high potential for application in multimodal bioimaging.

Safety assessment of new nanodiamonds@corrole hybrids addressed by the response of RAW-264.7 macrophages.

Safety assessment of carbon nanomaterials is of paramount importance since they are on the frontline for applications in sensing, bioimaging and drug delivery. The biocompatibility and safety of functionalized nanodiamonds (NDs) are here addressed through the study of the pro-inflammatory response of RAW-264.7 macrophages exposed to new nanodiamonds@corrole hybrids. The corrole unit selected is as a prototype for a hydrophobic organic molecule that can function as a NIR fluorophore reporter, an optical sensor, a photodynamic therapy agent or a photocatalyst. The new functional nanohybrids containing detonated nanodiamonds (NDs) were obtained through esterification using carboxylated NDs and glycol corroles. The success of the covalent functionalization via carbodiimide activation was confirmed through X-ray photoelectron spectroscopy (XPS), Raman and Fourier transform infrared (FTIR) spectroscopy. The UV-vis absorption and emission spectra of the hybrids are additive with respect to the corrole features. The cellular uptake, localization, cell viability and effects on immune cell activation of the new hybrids and of the precursors were carefully investigated using RAW-264.7 macrophages. Overall results showed that the ND@corrole hybrids had no pro-inflammatory effects on the RAW-264.7 macrophage cell line, making them an ideal candidate for a wide range of biomedical applications.

Activated lymphocytes and high liver expression of IFN-γ are associated with fulminant hepatic failure in patients.

BACKGROUND & AIMS: To study immunological mechanisms of fulminant hepatic failure (FHF) derived from extensive liver lesions, 14 patients with FHF induced by different aetiologies were investigated by observance of both lymphocyte phenotyping and cytokine levels. METHODS: Five patients bearing benign acute hepatitis B (AHB) and seven healthy liver donors (HC) were used as controls. Samples of liver and blood from both FHF patients and HC were obtained during transplantation procedures. Plasma levels of IL-1ß, IL-4, IL-6, IL-8, IL-10, IFN-γ, TNF-α, MCP-1, RANTES and MIP-1α were quantified using a multiplex immunoassay. Cell characterization was carried out by flow cytometry. IFN-γ staining was performed on liver sections using immunofluorescence methods. RESULTS: An increase of peripheral frequency of natural killer (NK) cells expressing early activation markers (CD69, HLA-DR and CD38) and adhesion molecule CD44 was observed in FHF patients. Elevated frequency of T lymphocytes CD4(+) and CD8(+) expressing CD38 and adhesion molecules CD29 and CD44 was also observed in FHF. Additionally, an increase of natural killer T cells (NKT) was detected in FHF patients. High plasma cytokine levels were not statistically different between FHF and AHB patients. In comparison to HC, a strong liver expression of IFN-γ was detected in FHF patients. The increased frequency of CD4(+) CD44(+) and IL-8 cytokine was found in patients with poor prognosis. CONCLUSIONS: These findings indicate the involvement of NK and NKT cells as well as T lymphocytes CD4(+) and CD8(+) in the inflammatory process inducing FHF, confirmed by the high hepatic expression of IFN-γ.

A Fluorescent Nanosensor for Silver (Ag+) and Mercury (Hg2+) Ions Using Eu (III)-Doped Carbon Dots.

Carbon dots doped with Eu3+ ions (Eu-Cdots) were prepared by a hydrothermal treatment, using citric acid and urea as precursors and Eu (NO3)3 as a europium source. The Eu3+ ions are strongly coordinated with the carboxylate groups at the surface of the Cdots and incorporated within the nanographene network in the carbon core. Vibrational spectroscopy provides evidence of such interaction with identification of bands assigned to the stretching of the Eu-O bond. Eu3+ doped Cdots have larger diameters then undoped Cdots, but they are divided into smaller domains of sp2 carbon. The UV-vis excitation spectrum provides evidence of energy transfer from the Cdots to the Eu3+. The luminescence spectrum shows the characteristic sharp peaks of Eu3+ in the red part of the visible spectrum and a broad emission of Cdots centered at 450 nm. The luminescence of the Cdots is strongly quenched by Hg2+ and Ag+, but not by other cations. The quenching mechanism differs significantly depending on the nature of the ion. Both the blue emission of Cdots and the red emission of Eu3+ are quenched in the presence of Hg2+ while only the emission of the Cdots is affected by the presence of Ag+. A ratiometric sensor can be built using the ratio of luminescence intensities of the Cdots to the Eu3+ peaks.

Combining metal nanoclusters and carbon nanomaterials: Opportunities and challenges in advanced nanohybrids.

The development of functional materials with uniquely advanced properties lies at the core of nanoscience and nanotechnology. From the myriad possible combinations of organic and/or inorganic blocks, hybrids combining metal nanoclusters and carbon nanomaterials have emerged as highly attractive colloidal materials for imaging, sensing (optical and electrochemical) and catalysis, among other applications. While the metal nanoclusters provide extraordinary luminescent and electronic properties, the carbon nanomaterials (of zero, one or two dimensions) convey versatility, as well as unique interfacial, electronic, thermal, optical, and mechanical properties, which altogether can be put to use for the desired application. Herein, we present an overview of the field, for experts and non-experts, encompassing the basic properties of the building blocks, a systematic view of the chemical preparation routes and physicochemical properties of the hybrids, and a critical analysis of their ongoing and emerging applications. Challenges and opportunities, including directions towards green chemistry approaches, are also discussed.

Evaluation of the Sealing Ability and Bond Strength of Two Endodontic Root Canal Sealers: An In Vitro Study.

BACKGROUND: Obturation represents a critical step in endodontic treatment, which relies on a core material and a sealer. This study aims to evaluate the sealing ability and bond strength to the root canal walls of an epoxy resin-based sealer (AH-Plus®, Dentsply Sirona, Johnson City, TN, USA) and a bioceramic sealer (GuttaFlow Bioseal®, Coltène/Whaledent, GmbH + Co. KG, Langenau, Germany). METHODS: Thirty-eight maxillary anterior teeth with single roots and identical round sections were separated into two experimental groups according to the root canal sealers used, namely, G1 = AH-Plus® and G2 = GuttaFlow Bioseal®, and two control groups, specifically, G3 = the negative control and G4 = the positive control. The sealing capacity was measured by the penetration of the radioactive isotope 99mTc. For the push-out test, the compressive force test was performed in a universal machine and the force was applied by exerting pressure on the surface of the material to be tested in the apical to the coronal direction and using three test points with different diameters. RESULTS: GuttaFlow Bioseal® exhibited superior sealing ability compared to AH-Plus® (p = 0.003). Regarding the bond strength, AH-Plus® provided higher adhesion values than GuttaFlow Bioseal® in the three sections of the tooth root (p = 0.001). CONCLUSIONS: GuttaFlow Bioseal® had significantly better sealing ability than AH-Plus® but lower adhesion values in the three zones of the root canal, with statistically significant differences between the groups. However, it is important to note that for the action of endodontic sealers to be maximized, the root-filling technique must be most appropriate.

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core.

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.

Nanopatterning in Langmuir-Blodgett monolayers of a thermoresponsive double hydrophilic block copolymer studied by atomic force microscopy.

The microphase-separation of Langmuir-Blodgett (LB) monolayers of a rhodamine B (RhB) end-labeled double hydrophilic block copolymer (DHBC), RhB-Poly(N,N-dimethylacrylamide)-b-poly(N,N-diethylacryl-amide) (RhB-PDMA(207)b-PDEA177) and the 1:1 segmental mixture of PDEA and RhB-PDMA homopolymers was followed by AFM. The DHBC LB films revealed a loose distribution of nano-aggregates with variable geometries below the lower critical solution temperature (LCST) of PDEA (32 degrees C) and low surface pressure (3 mN m(-1)). By increasing either the temperature above the LCST of PDEA or the surface pressure beyond the immersion regime of PDMA in the subphase (7 mN m(-1)) a dense nanopatterning was obtained. The absence of a corresponding regular nanopatterning in LB films of mixed homopolymers with the same composition highlights the role of the covalent bonding between PDEA and PDMA on the self-segregation of the two blocks at the air-water interface.