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1.
Nature ; 609(7929): 1029-1037, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-36104562

RESUMO

Advancing the spontaneous bottom-up construction of artificial cells with high organizational complexity and diverse functionality remains an unresolved issue at the interface between living and non-living matter1-4. Here, to address this challenge, we developed a living material assembly process based on the capture and on-site processing of spatially segregated bacterial colonies within individual coacervate microdroplets for the endogenous construction of membrane-bounded, molecularly crowded, and compositionally, structurally and morphologically complex synthetic cells. The bacteriogenic protocells inherit diverse biological components, exhibit multifunctional cytomimetic properties and can be endogenously remodelled to include a spatially partitioned DNA-histone nucleus-like condensate, membranized water vacuoles and a three-dimensional network of F-actin proto-cytoskeletal filaments. The ensemble is biochemically energized by ATP production derived from implanted live Escherichia coli cells to produce a cellular bionic system with amoeba-like external morphology and integrated life-like properties. Our results demonstrate a bacteriogenic strategy for the bottom-up construction of functional protoliving microdevices and provide opportunities for the fabrication of new synthetic cell modules and augmented living/synthetic cell constructs with potential applications in engineered synthetic biology and biotechnology.


Assuntos
Células Artificiais , Escherichia coli , Viabilidade Microbiana , Biologia Sintética , Citoesqueleto de Actina/química , Actinas/química , Trifosfato de Adenosina/metabolismo , Células Artificiais/química , Biotecnologia , Escherichia coli/citologia , Histonas/química , Vacúolos/química , Água/química
2.
Nature ; 601(7891): 45-48, 2022 01.
Artigo em Inglês | MEDLINE | ID: mdl-34987215

RESUMO

Stellar ejecta gradually enrich the gas out of which subsequent stars form, making the least chemically enriched stellar systems direct fossils of structures formed in the early Universe1. Although a few hundred stars with metal content below 1,000th of the solar iron content are known in the Galaxy2-4, none of them inhabit globular clusters, some of the oldest known stellar structures. These show metal content of at least approximately 0.2% of the solar metallicity [Formula: see text]. This metallicity floor appears universal5,6, and it has been proposed that protogalaxies that merged into the galaxies we observe today were simply not massive enough to form clusters that survived to the present day7. Here we report observations of a stellar stream, C-19, whose metallicity is less than 0.05% of the solar metallicity [Formula: see text]. The low metallicity dispersion and the chemical abundances of the C-19 stars show that this stream is the tidal remnant of the most metal-poor globular cluster ever discovered, and is significantly below the purported metallicity floor: clusters with significantly lower metallicities than observed today existed in the past and contributed their stars to the Milky Way halo.

3.
Nature ; 574(7776): 69-71, 2019 10.
Artigo em Inglês | MEDLINE | ID: mdl-31578482

RESUMO

Large galaxies grow through the accumulation of dwarf galaxies1,2. In principle it is possible to trace this growth history via the properties of a galaxy's stellar halo3-5. Previous investigations of the galaxy Messier 31 (M31, Andromeda) have shown that outside a galactocentric radius of 25 kiloparsecs the population of halo globular clusters is rotating in alignment with the stellar disk6,7, as are more centrally located clusters8,9. The M31 halo also contains coherent stellar substructures, along with a smoothly distributed stellar component10-12. Many of the globular clusters outside a radius of 25 kiloparsecs are associated with the most prominent substructures, but some are part of the smooth halo13. Here we report an analysis of the kinematics of these globular clusters. We find two distinct populations rotating perpendicular to each other. The rotation axis for the population associated with the smooth halo is aligned with the rotation axis for the plane of dwarf galaxies14 that encircles M31. We interpret these separate cluster populations as arising from two major accretion epochs, probably separated by billions of years. Stellar substructures from the first epoch are gone, but those from the more recent second epoch still remain.

4.
Nano Lett ; 24(27): 8296-8302, 2024 Jul 10.
Artigo em Inglês | MEDLINE | ID: mdl-38920284

RESUMO

Chirality is inherent to a broad range of systems, including solid-state and wave physics. The precession (chiral motion) of the magnetic moments in magnetic materials, forming spin waves, has various properties and many applications in magnetism and spintronics. We show that an optical analogue of spin waves can be generated in arrays of plasmonic nanohelices. Such optical waves arise from the interaction between twisted helix eigenmodes carrying spin and orbital angular momenta. We demonstrate that these optical spin waves are reflected at the interface between successive domains of enantiomeric nanohelices, forming a heterochiral lattice regardless of the wave propagation direction within the lattice. Optical spin waves may be applied in techniques involving photon spin, ranging from data processing and storage to quantum optics.

5.
Eur J Nucl Med Mol Imaging ; 51(12): 3696-3708, 2024 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-38896129

RESUMO

AIM: To determine the long-term prognosis of immune-related response profiles (pseudoprogression and dissociated response), not covered by conventional PERCIST criteria, in patients with non-small-cell lung cancer (NSCLC) treated with immune checkpoint inhibitors (ICPIs). METHODS: 109 patients were prospectively included and underwent [18F]FDG-PET/CT at baseline, after 7 weeks (PETinterim1), and 3 months (PETinterim2) of treatment. On PETinterim1, tumor response was assessed using standard PERCIST criteria. In the event of PERCIST progression at this time-point, the study design provided for continued immunotherapy for 6 more weeks. Additional response patterns were then considered on PETinterim2: pseudo-progression (PsPD, subsequent metabolic response); dissociated response (DR, coexistence of responding and non-responding lesions), and confirmed progressive metabolic disease (cPMD, subsequent homogeneous progression of lesions). Patients were followed up for at least 12 months. RESULTS: Median follow-up was 21 months. At PETinterim1, PERCIST progression was observed in 60% (66/109) of patients and ICPI was continued in 59/66. At the subsequent PETinterim2, 14% of patients showed PsPD, 11% DR, 35% cPMD, and 28% had a sustained metabolic response. Median overall survival (OS) and progression-free-survival (PFS) did not differ between PsPD and DR (27 vs 29 months, p = 1.0; 17 vs 12 months, p = 0.2, respectively). The OS and PFS of PsPD/DR patients were significantly better than those with cPMD (29 vs 9 months, p < 0.02; 16 vs 2 months, p < 0.001), but worse than those with sustained metabolic response (p < 0.001). This 3-group prognostic stratification enabled better identification of true progressors, outperforming the prognostic value of standard PERCIST criteria (p = 0.03). CONCLUSION: [18F]FDG-PET/CT enables early assessment of response to immunotherapy. The new wsPERCIST ("wait and see") PET criteria proposed, comprising immune-related atypical response patterns, can refine conventional prognostic stratification based on PERCIST criteria. TRIAL REGISTRATION: HDH F20230309081206. Registered 20 April 2023. Retrospectively registered.


Assuntos
Carcinoma Pulmonar de Células não Pequenas , Fluordesoxiglucose F18 , Imunoterapia , Neoplasias Pulmonares , Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada , Humanos , Carcinoma Pulmonar de Células não Pequenas/diagnóstico por imagem , Carcinoma Pulmonar de Células não Pequenas/terapia , Masculino , Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/terapia , Feminino , Idoso , Pessoa de Meia-Idade , Prognóstico , Resultado do Tratamento , Idoso de 80 Anos ou mais , Adulto
6.
Caries Res ; : 1-11, 2024 May 30.
Artigo em Inglês | MEDLINE | ID: mdl-38815561

RESUMO

INTRODUCTION: Cariogenic bacterial acids dissolve the inorganic elements in dentine, leaving the dentine matrix exposed. Host-derived matrix metalloproteinases (MMPs) play an essential role in caries progression as they are significant regulators of extracellular matrix turnover and can degrade exposed collagen. This paper investigates the expression of MMP2 and MMP9 across various stages of caries in primary human teeth and relate this with a diagnosis recorded by the International Caries Detection and Assessment System (ICDAS). METHODS: Twenty-four sections (150 µm in thickness) from extracted teeth, clinically diagnosed using ICDAS, were immunohistochemically treated with monoclonal anti-MMP2 and anti-MMP9 antibodies. Positive staining was visualised by immunofluorescence using a VectorFluor Duet Double Labeling Kit. Images from triplicate samples for each ICDAS score were analysed using ImageJ software. Collagen degradation in caries lesions was detected using a hydroxyproline assay. RESULTS: MMPs were weakly detected in caries with ICDAS 1-2 scores, and an insignificant increase was detected in ICDAS 3. However, a significant increase in MMP expression was seen in caries with an ICDAS score of 4-6. There was a strong positive correlation between the ICDAS score and MMP2 (r [6] = 0.86, p = 0.002) and between ICDAS and MMP9 (r [6] = 0.82, p = 0.004). Data were analysed using two-way ANOVA followed by Tukey multiple comparison test (*p < 0.05). CONCLUSION: The use of ICDAS to assess the severity of caries lesions and how this correlates with the presence of MMP in these lesions validates the modern approach to caries management with a minimally invasive concept.

7.
Eur J Dent Educ ; 28(4): 969-977, 2024 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-39136094

RESUMO

INTRODUCTION: This paper reports on the scholarship activity of the 'Sustainability in Dentistry' Special-interest Group (SiG), which met at the Association for Dental Education in Europe (ADEE) annual conference in Liverpool on 25 August 2023. The aim of this study was to (i) identify current teaching practices and approaches to embedding Environmental Sustainability (ES) in the curriculum in ADEE attendee schools and (ii) explore existing barriers/challenges to incorporating ES in dental education and consider potential solutions. METHODOLOGY: A mixed-methods approach was used to fulfil the aims of this study. A pre-workshop questionnaire was used to explore current teaching practices, challenges and drivers of embedding ES in the curriculum. An interactive workshop at the in-person meeting in Liverpool was used to propose key strategies to overcome the most frequent challenges to embedding ES in the curriculum. RESULTS: The majority of respondents (56%) reported that their institutions do not currently teach ES. Traditional didactic forms of teaching were mostly reported to teach ES in non-clinical environments, and a transition to more environmentally sustainable materials and instruments was the most popular response for clinical teaching. Key barriers to embedding ES in the curriculum were identified, including time constraints and the overloaded curriculum, a lack of expertise/knowledge to teach and lack of practical guidance to support educators, limited learning resources for staff and students and resistance from colleagues regarding the relevance of ES in dentistry. The special-interest group participants proposed strategies to overcome these challenges that centred around 14 themes. CONCLUSION: This paper reports recent scholarship activity by ADEE's 'Sustainability in Dentistry' SiG. Key strategies for overcoming the most common challenges to embedding ES in the curriculum are also discussed.


Assuntos
Conservação dos Recursos Naturais , Currículo , Educação em Odontologia , Educação em Odontologia/métodos , Humanos , Europa (Continente) , Inquéritos e Questionários
8.
Angew Chem Int Ed Engl ; 63(36): e202409780, 2024 Sep 02.
Artigo em Inglês | MEDLINE | ID: mdl-38873877

RESUMO

Transient melting of the duplex-DNA (B-DNA) during DNA transactions allows repeated sequences to fold into non-B-DNA structures, including DNA junctions and G-quadruplexes. These noncanonical structures can act as impediments to DNA polymerase progression along the duplex, thereby triggering DNA damage and ultimately jeopardizing genomic stability. Their stabilization by ad hoc ligands is currently being explored as a putative anticancer strategy since it might represent an efficient way to inflict toxic DNA damage specifically to rapidly dividing cancer cells. The relevance of this strategy is only emerging for three-way DNA junctions (TWJs) and, to date, no molecule has been recognized as a reference TWJ ligand, featuring both high affinity and selectivity. Herein, we characterize such reference ligands through a combination of in vitro techniques comprising affinity and selectivity assays (competitive FRET-melting and TWJ Screen assays), functional tests (qPCR and Taq stop assays) and structural analyses (molecular dynamics and NMR investigations). We identify novel azacryptands TrisNP-amphi and TrisNP-ana as the most promising ligands, interacting with TWJs with high affinity and selectivity. These ligands represent new molecular tools to investigate the cellular roles of TWJs and explore how they can be exploited in innovative anticancer therapies.


Assuntos
DNA , DNA/química , Ligantes , Estrutura Molecular , Simulação de Dinâmica Molecular , Conformação de Ácido Nucleico , Humanos , Quadruplex G , Transferência Ressonante de Energia de Fluorescência
9.
BMC Biol ; 20(1): 8, 2022 01 07.
Artigo em Inglês | MEDLINE | ID: mdl-34996449

RESUMO

BACKGROUND: The application of CRISPR/Cas9 technology in human induced pluripotent stem cells (hiPSC) holds tremendous potential for basic research and cell-based gene therapy. However, the fulfillment of these promises relies on the capacity to efficiently deliver exogenous nucleic acids and harness the repair mechanisms induced by the nuclease activity in order to knock-out or repair targeted genes. Moreover, transient delivery should be preferred to avoid persistent nuclease activity and to decrease the risk of off-target events. We recently developed bacteriophage-chimeric retrovirus-like particles that exploit the properties of bacteriophage coat proteins to package exogenous RNA, and the benefits of lentiviral transduction to achieve highly efficient, non-integrative RNA delivery in human cells. Here, we investigated the potential of bacteriophage-chimeric retrovirus-like particles for the non-integrative delivery of RNA molecules in hiPSC for CRISPR/Cas9 applications. RESULTS: We found that these particles efficiently convey RNA molecules for transient expression in hiPSC, with minimal toxicity and without affecting the cell pluripotency and subsequent differentiation. We then used this system to transiently deliver in a single step the CRISPR-Cas9 components (Cas9 mRNA and sgRNA) to generate gene knockout with high indel rate (up to 85%) at multiple loci. Strikingly, when using an allele-specific sgRNA at a locus harboring compound heterozygous mutations, the targeted allele was not altered by NHEJ/MMEJ, but was repaired at high frequency using the homologous wild type allele, i.e., by interallelic gene conversion. CONCLUSIONS: Our results highlight the potential of bacteriophage-chimeric retrovirus-like particles to efficiently and safely deliver RNA molecules in hiPSC, and describe for the first time genome engineering by gene conversion in hiPSC. Harnessing this DNA repair mechanism could facilitate the therapeutic correction of human genetic disorders in hiPSC.


Assuntos
Bacteriófagos , Células-Tronco Pluripotentes Induzidas , Alelos , Bacteriófagos/genética , Sistemas CRISPR-Cas , Conversão Gênica , Edição de Genes/métodos , Técnicas de Inativação de Genes , Humanos , Células-Tronco Pluripotentes Induzidas/metabolismo , RNA/metabolismo , Retroviridae/genética
10.
Eur J Dent Educ ; 27(3): 650-661, 2023 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-36121067

RESUMO

The FDI World Dental Federation suggests that "dentistry, as a profession, should integrate Sustainable Development Goals into daily practice and support a shift to a green economy in the pursuit of healthy lives and wellbeing for all, through all stages of life." This article reports on the recent activity of the Association for Dental Education in Europe Special Interest Group for Sustainability in Dentistry. Following on from the group's previous activities, which explored current educational practice, this work aimed to reach a pan-European consensus on a number of learning outcomes for environmental sustainability, in order to (i) support institutions in designing and delivering their curriculum, and (ii) to further harmonise the delivery of oral health professional education across Europe. This article presents specific learning outcomes relating to environmental sustainability and recommendations relating to curriculum development, including methods of teaching and assessment.


Assuntos
Educação em Odontologia , Saúde Bucal , Humanos , Currículo , Aprendizagem , Europa (Continente) , Ensino
11.
J Am Chem Soc ; 144(6): 2816-2824, 2022 02 16.
Artigo em Inglês | MEDLINE | ID: mdl-35113550

RESUMO

Zirconium and hafnium in the tetravalent oxidation state are considered the two most similar elements on the periodic table, based on their coexistence in nature and their identical solid-state chemistry. However, differentiating solution phase chemistry is crucial for their separation for nuclear applications that exploit the neutron capture of Hf and neutron transparency of Zr. Here we provide molecular level detail of the multiple factors that influence Zr/Hf separation in a long-exploited, empirically designed industrial solvent-extraction process that favors Hf extraction into an organic phase. In the aqueous solution, both Hf and Zr form an oxo-centered tetramer cluster with a core formula of [OM4(OH)6(NCS)12]4- (OM4-NCS, M = Hf, Zr). This was identified by single-crystal X-ray diffraction, as well as small-angle X-ray scattering (SAXS), of both the aqueous and organic phase. In addition to this phase, Zr also forms (1) a large oxo-cluster formulated [Zr48O30(OH)92(NCS)40(H2O)40] (Zr48) and (2) NCS adducts of OZr4-NCS. Zr48 was identified first by SAXS and then crystallized by exploiting favorable soft-metal bonding to the sulfur of NCS. While the large Zr48 likely cannot be extracted due to its larger size, the NCS adducts of OZr4-NCS are also less favorable to extraction due to the extra negative charge, which necessitates coextraction of an additional countercation (NH4+) per extra NCS ligand. Differentiating Zr and Hf coordination and hydrolysis chemistry adds to our growing understanding that these two elements, beyond simple solid-state chemistry, have notable differences in chemical reactivity.

12.
Eur J Nucl Med Mol Imaging ; 49(11): 3878-3891, 2022 09.
Artigo em Inglês | MEDLINE | ID: mdl-35562529

RESUMO

PURPOSE: We evaluated the prognostic value of immunotherapy-induced organ inflammation observed on 18FDG PET in patients with non-small cell lung cancer (NSCLC) treated with immune checkpoint inhibitors (ICPIs). METHODS: Data from patients with IIIB/IV NSCLC included in two different prospective trials were analyzed. 18FDG PET/CT exams were performed at baseline (PETBaseline) and repeated after 7-8 weeks (PETInterim1) and 12-16 weeks (PETInterim2) of treatment, using iPERCIST for tumor response evaluation. The occurrence of abnormal organ 18FDG uptake, deemed to be due to ICPI-related organ inflammation, was collected. RESULTS: Exploratory cohort (Nice, France): PETInterim1 and PETInterim2 revealed the occurrence of at least one ICPI-induced organ inflammation in 72.8% of patients, including midgut/hindgut inflammation (33.7%), gastritis (21.7%), thyroiditis (18.5%), pneumonitis (17.4%), and other organ inflammations (9.8%). iPERCIST tumor response was associated with improved progression-free survival (p < 0.001). iPERCIST tumor response and immuno-induced gastritis assessed on PET were both associated with improved overall survival (OS) (p < 0.001 and p = 0.032). Combining these two independent variables, we built a model predicting patients' 2-year OS with a sensitivity of 80.3% and a specificity of 69.2% (AUC = 72.7). Validation cohort (Genova, Italy): Immuno-induced gastritis (19.6% of patients) was associated with improved OS (p = 0.04). The model built previously predicted 2-year OS with a sensitivity and specificity of 72.0% and 63.6% (AUC = 70.7) and 3-year OS with a sensitivity and specificity of 69.2% and 80.0% (AUC = 78.2). CONCLUSION: Immuno-induced gastritis revealed by early interim 18FDG PET in around 20% of patients with NSCLC treated with ICPI is a novel and reproducible imaging biomarker of improved OS.


Assuntos
Carcinoma Pulmonar de Células não Pequenas , Gastrite , Neoplasias Pulmonares , Carcinoma Pulmonar de Células não Pequenas/diagnóstico por imagem , Carcinoma Pulmonar de Células não Pequenas/terapia , Fluordesoxiglucose F18 , Humanos , Fatores Imunológicos , Imunoterapia/efeitos adversos , Inflamação/diagnóstico por imagem , Neoplasias Pulmonares/diagnóstico por imagem , Neoplasias Pulmonares/terapia , Tomografia por Emissão de Pósitrons combinada à Tomografia Computadorizada/métodos , Prognóstico , Estudos Prospectivos , Estudos Retrospectivos
13.
J Evol Biol ; 35(5): 669-679, 2022 05.
Artigo em Inglês | MEDLINE | ID: mdl-35290678

RESUMO

Variational properties hold a fundamental role in shaping biological evolution, exerting control over the magnitude and direction of evolutionary change elicited by microevolutionary processes that sort variation, such as selection or drift. We studied the genus Tyrannus as a model for examining the conditions and drivers that facilitate the repeated evolution of exaggerated, secondary sexual traits in the face of significant functional limitations. In particular, we explore the role of allometry, sexual selection and their interaction, on the diversification of tail morphology in the genus, assessing whether and how they promoted or constrained phenotypic evolution. Non-deep-forked species tend to show reduced sexual dimorphism and moderate allometric variation in tail shape. The exaggerated and functionally constrained long feathers of deep-forked species, T. savana and T. forficatus, which show both marked sexual dimorphism and allometric tail shape variation, independently diverged from the rest of the genus following the same direction of main interspecific variation accrued during the evolution of non-deep-forked species. Moreover, the latter direction is also aligned with axes summarising sexual dimorphism and allometric variation on deep-forked species, a feature lacking in the rest of the species. Thus, exaggerated tail morphologies are interpreted as the result of amplified divergence through reorientation and co-option of allometric variation by sexual selection, repeatedly driving morphology along a historically favoured direction of cladogenetic evolution.


Assuntos
Caracteres Sexuais , Seleção Sexual , Animais , Evolução Biológica , Plumas/anatomia & histologia , Cabeça/anatomia & histologia
14.
Inorg Chem ; 61(8): 3586-3597, 2022 Feb 28.
Artigo em Inglês | MEDLINE | ID: mdl-35148102

RESUMO

Synthesizing functional materials from water contributes to a sustainable energy future. On the atomic level, water drives complex metal hydrolysis/condensation/speciation, acid-base, ion pairing, and solvation reactions that ultimately direct material assembly pathways. Here, we demonstrate the importance of Nb-polyoxometalate (Nb-POM) speciation in enabling deposition of Nb2O5, LiNbO3, and (Na, K)NbO3 (KNN) from high-concentration solutions, up to 2.5 M Nb for Nb2O5 and ∼1 M Nb for LiNbO3 and KNN. Deposition of KNN from 1 M Nb concentration represents a potentially important advancment in lead-free piezoelectrics, an application that requires thick films. Solution characterization via small-angle X-ray scattering and Raman spectroscopy described the speciation for all precursor solutions as the [HxNb24O72](x-24) POM, as did total pair distribution function analyses of X-ray scattering of amorphous gels prior to conversion to oxides. The tendency of the Nb24-POM to form extended networks without crystallization leads to conformal and well-adhered films. The films were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, ellipsometry, and X-ray photoelectron spectroscopy. As a strategy to convert aqueous deposition solutions from {Nb10}-POMs to {Nb24}-POMs, we devised a general procedure to produce doped Nb2O5 thin films including Ca, Ag, and Cu doping.

15.
Inorg Chem ; 61(3): 1275-1286, 2022 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-35005894

RESUMO

Deoxycholic acid (DOC) is a unique, biologically derived surfactant with facial amphiphilicity that has been exploited, albeit minimally, in supramolecular assembly of materials. Here, we present the synthesis and structural characterization of three hybrid metal (Zn2+ and Cd2+)-DOC compounds. Analysis by single-crystal X-ray diffraction reveals the many interactions that are possible between these facial surfactants and the influence of solvent molecules that drive the assembly of materials. These structures are the first metal-DOC complexes besides those obtained from alkali and alkaline earth metals. We isolated polymeric chains of both Cd and Zn (Znpoly-DOC and Cdpoly-DOC) from water. Major interactions between DOC molecules in these phases are hydrophobic in nature. Cdpoly-DOC exhibits unique P1 symmetry, with complete interdigitation of the amphiphiles between neighboring polymeric chains. Zn4-DOC, obtained from methanol dissolution of Znpoly-DOC, features the OZn4 tetrahedron, widely known in basic zinc acetate and MOF-5 (metal organic framework). We document a solvent-driven, room-temperature transition between Znpoly-DOC and Zn4-DOC (in both directions) by scanning and transmission electron microscopies in addition to small-angle X-ray scattering, powder X-ray diffraction, and infrared spectroscopy. These studies show the methanol-driven transition of Znpoly-DOC to Zn4-DOC occurs via an intermediate with no long-range order of the Zn4 clusters, indicating the strongest interactions driving assembly are intramolecular. On the contrary, water-driven solid-to-solid transformation from Zn4-DOC to Znpoly-DOC exhibits crystal-to-crystal transformation. Znpoly-DOC is robust, easy to synthesize, and comprised of biologically benign components, so we demonstrate dye absorption as a proxy for water treatment applications. It favors absorption of positively charged dyes. These studies advance molecular level knowledge of the supramolecular assembly of facial surfactants that can be exploited in the design of organic-inorganic hybrid materials. This work also highlights the potential of solvent for tuning supramolecular assembly processes, leading to new hybrid materials featuring facial surfactants.

16.
Ecotoxicol Environ Saf ; 243: 113984, 2022 Sep 15.
Artigo em Inglês | MEDLINE | ID: mdl-35988383

RESUMO

Aquatic environments have been found to be contaminated with a variety of inorganic and organic UV filters. This includes novel nano-sized titanium dioxide (TiO2) composite particles, which have been increasingly developed and incorporated into commercial sunscreens in recent years. So far, relatively little is known about the effects of this novel class of UV filters on aquatic life. Therefore, this study aimed to determine and compare the toxicity of three such nanoparticulate TiO2 UV filters with different surface coatings, namely Eusolex® T-Avo (SiO2-coated), T-Lite™ SF (Al(OH)3/PDMS-coated), and Eusolex® T-S (Al2O3/stearic acid-coated) either alone, or in the presence of selected organic UV filters (octinoxate, avobenzone, octocrylene), toward fish using RTgill-W1 cell cultures as an in vitro experimental model. Besides standard exposure protocols, alternative approaches (i.e., exposure to water accommodated fractions (WAFs), hanging-drop exposure) were explored to account for nanoparticle (NP)-specific fate in the medium and obtain additional/complementary information on their toxicity in different conditions. The AlamarBlue, CFDA-AM and Neutral Red Retention (NR) assays were used to measure effects on different cellular endpoints. Transmission electron microscopy (TEM) was used to examine NP uptake. Our results showed that none of the TiO2 NP UV filters were cytotoxic at the concentrations tested (0.1-10 µg/mL; 24 h) but there were differences in their uptake by the cells. Thus, only the hydrophilic T-AVO was detected inside cells, but the hydrophobic T-Lite SF and T-S were not. In addition, our results show that the presence of NPs (or the used dispersant) tended to decrease organic UV filter toxicity. The level of combination effect depended on both NP-type (surface chemistry) and concentration, suggesting that the reduced toxicity resulted from reduced availability of the organic UV filters due to their adsorption to the NP surface. Thus, mixtures of TiO2 NP UV filters and organic UV filters may have a different toxicological profile compared to the single substances, but probably do not pose an increased hazard.


Assuntos
Brânquias , Nanocompostos , Animais , Peixes , Dióxido de Silício , Protetores Solares/química , Protetores Solares/toxicidade , Titânio/química , Titânio/toxicidade
17.
Nano Lett ; 21(8): 3410-3417, 2021 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-33830778

RESUMO

A wide variety of optical applications and techniques require control of light polarization. So far, the manipulation of light polarization relies on components capable of interchanging two polarization states of the transverse field of a propagating wave (e.g., linear to circular polarizations, and vice versa). Here, we demonstrate that an individual helical nanoantenna is capable of locally converting longitudinally oriented confined near-fields into a circularly polarized freely propagating wave, and vice versa. To this end, the nanoantenna is coupled to cylindrical surface plasmons bound to the top interface of a thin gold layer. Helices of constant and varying pitch lengths are experimentally investigated. The reciprocal conversion of an incoming circularly wave into diverging cylindrical surface plasmons is demonstrated as well. Interconnecting circularly polarized optical waves (carrying spin angular momentum) and longitudinal near-fields provides a new degree of freedom in light polarization control.

18.
Molecules ; 27(22)2022 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-36431929

RESUMO

Mesoscopic shear elasticity has been revealed in ordinary liquids both experimentally by reinforcing the liquid/surface interfacial energy and theoretically by nonextensive models. The elastic effects are here examined in the frame of small molecules with strong electrostatic interactions such as room temperature ionic liquids [emim][Tf2N] and nitrate solutions exhibiting paramagnetic properties. We first show that these charged fluids also exhibit a nonzero low-frequency shear elasticity at the submillimeter scale, highlighting their resistance to shear stress. A neutron scattering study completes the dynamic mechanical analysis of the paramagnetic nitrate solution, evidencing that the magnetic properties do not induce the formation of a structure in the solution. We conclude that the elastic correlations contained in liquids usually considered as viscous away from any phase transition contribute in an effective way to collective effects under external stress whether mechanical or magnetic fields.

19.
Eur J Dent Educ ; 26(2): 393-403, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-34498360

RESUMO

INTRODUCTION: Students face a number of challenges in translating the skills acquired in pre-clinical simulation environments to the delivery of real patient care. These are particularly emphasised for complex operative procedures such as tooth preparations for indirect restorations. This paper reports student perceptions of a novel approach designed to improving student confidence when undertaking operative procedures on patients for the first time, by providing patient-specific simulation using virtual reality (VR) and 3D-printed models of the student's real clinical case. MATERIALS AND METHODS: Students practised on patient-specific models, in the presence of a clinical tutor, firstly using VR simulation then with 3D-printed models in a clinical skills laboratory. The students then carried out the operative procedure on their patients, on the third occasion of practice. After providing the treatment for their patients, students attended a semi-structured interview to discuss their experiences. The qualitative data were analysed using two forms of inductive analysis. RESULTS: Students most frequently cited: the value of the educator, increased confidence and efficiency during the clinical procedure, improved patient confidence and the complementary benefits of the two simulation modalities. Thematic analysis of participants' responses uncovered five key themes: The value of virtual reality dental simulators The value of clinical skills laboratory simulation with 3D-printed models The value of educator engagement The impact on the clinical procedure and the patient The VR and clinical skills laboratory balance CONCLUSION: This paper reports the early findings of an intervention that improves dental student confidence through the use of patient-specific VR exercises and 3D-printed models. These provided an incremental learning experience for an operative clinical procedure, prior to treatment of the live patient. Early results suggest this is a positive experience for the students, providing a valuable contribution to their confidence and preparedness.


Assuntos
Educação em Odontologia , Realidade Virtual , Competência Clínica , Humanos , Impressão Tridimensional , Estudantes
20.
Angew Chem Int Ed Engl ; 61(19): e202117839, 2022 May 02.
Artigo em Inglês | MEDLINE | ID: mdl-35148455

RESUMO

Polyoxometalates (POMs), ranging in size from 1 to 10's of nanometers, resemble building blocks of inorganic materials. Elucidating their complex solubility behavior with alkali-counterions can inform natural and synthetic aqueous processes. In the study of POMs ([Nb24 O72 H9 ]15- , Nb24 ) we discovered an unusual solubility trend (termed anomalous solubility) of alkali-POMs, in which Nb24 is most soluble with the smallest (Li+ ) and largest (Rb/Cs+ ) alkalis, and least soluble with Na/K+ . Via computation, we define a descriptor (σ-profile) and use an artificial neural network (ANN) to predict all three described alkali-anion solubility trends: amphoteric, normal (Li+ >Na+ >K+ >Rb+ >Cs+ ), and anomalous (Cs+ >Rb+ >K+ >Na+ >Li+ ). Testing predicted amphoteric solubility affirmed the accuracy of the descriptor, provided solution-phase snapshots of alkali-POM interactions, yielded a new POM formulated [Ti6 Nb14 O54 ]14- , and provides guidelines to exploit alkali-POM interactions for new POMs discovery.

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